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Pressure dependence of the oxygen reduction reaction at the platinum microelectrode/nafion interface - Electrode kinetics and mass transport

The investigation of oxygen reduction kinetics at the platinum/Nafion interface is of great importance in the advancement of proton-exchange-membrane (PEM) fuel-cell technology. This study focuses on the dependence of the oxygen reduction kinetics on oxygen pressure. Conventional Tafel analysis of the data shows that the reaction order with respect to oxygen is unity at both high and low current densities. Chronoamperometric measurements of the transport parameters for oxygen in Nafion show that oxygen dissolution follows Henry's isotherm. The diffusion coefficient of oxygen is invariant with pressure; however, the diffusion coefficient for oxygen is lower when air is used as the equilibrating gas as compared to when oxygen is used for equilibration. These results are of value in understanding the influence of O2 partial pressure on the performance of PEM fuel cells and also in elucidating the mechanism of oxygen reduction at the platinum/Nafion interface.

Parthasarathy, Arvind↗

Regenerative fuel cells

A development status evaluation is presented for moderate-temperature, single-unit, regenerative fuel cells using either alkaline or solid polymer proton-exchange membrane (PEM) electrolytes. Attention is given to the results thus far obtained for Pt, Ir, Rh, and Na(x)Pt3O4 catalysts. Alkaline electrolyte tests have been performed on a half-cell basis with a floating-electrode cell; PEM testing has been with complete fuel cells, using Nafion 117.

Swette, Larry L.↗

The UARS particle environment monitor

The overall objective of the particle environment monitor (PEM) is to provide comprehensive measurements of both local and global energy inputs into the earth's atmosphere by charged particles and Joule dissipation using a carefully integrated set of instruments. PEM consists of four instruments: the atmospheric X-ray imaging spectrometer (AXIS), the high-energy particle spectrometer (HEPS), the medium-energy particle spectrometer (MEPS), and the vector magnetometer (VMAG). AXIS provides global scale images and energy spectra of 3- to 100-keV bremsstrahlung X-rays produced by electron precipitation into the atmosphere. HEPS and MEPS provide in situ measurements of precipitating electrons in the energy range from 1 eV to 5 MeV and protons in the energy range from 1 eV to 150 MeV. Particles in this energy range deposit their energy in the atmosphere at altitudes extending from several hundred kilometers down to as low as about 30 km. VMAG provides the magnetic field direction needed to indicate and interpret the locations and intensities of ionospheric and field-aligned currents as well as providing a reference for the particle measurements. Examples of data acquired early in the Upper Atmosphere Research Satellite (UARS) mission are presented.

Winningham, J. D.↗

Observations of the UARS Particle Environment Monitor and computation of ionization rates in the middle and upper atmosphere during a geomagnetic storm

In this paper we present observations made by the Particle Environment Monitor (PEM) instruments during the geomagnetic storm of 8-9 November, 1991. Ionization and energy deposition rates as functions of altitude in the middle and upper atmosphere by incident electrons and positive ions in the storm interval are computed. The suite of PEM instruments provides a systematic measurement of energetic particles and their associated X-rays over an energy range not fully covered by previous satellite missions.

Sharber, J. R.↗

Asian Influence Over the Western North Pacific during the Fall Season: Inferences from Lead 210, Soluble Ionic Species and Ozone

Aerosol samples collected over the western Pacific during the NASA/Global Tropospheric Experiment Pacific Exploratory Mission (PEM-West A) expedition (September - October 1991) revealed mean Pb-210 concentrations in the free troposphere in the 5-10 fCi m(exp -3) STP range. Most soluble ionic aerosol-associated species were near detection limits [much less than 40 parts per trillion by volume (pptv)] in these same samples. The altitude distribution of O3 near Asia closely resembled that of Pb-210, while no relationship was found between the concentrations of O3 and Be-7. Free tropospheric air over the western Pacific was depleted in soluble aerosol-associated species but enriched in Pb-210 and O3, indicative of deep wet convection over the Asian continent. The influence of Asian air on the composition of the free troposphere over the western Pacific was evident on most of the PEM-West A flights. However, evidence of continental influence was largely restricted to those species that are relatively insoluble (or have insoluble precursors), hence escape scavenging during vertical transport from the boundary layer into the free troposphere by wet convective activity.

Dibb, J. E.↗

Implications of Large Scale Shifts in Tropospheric NO(x) Levels in the Remote Tropical Pacific

A major observation recorded during NASA's western Pacific Exploratory Mission (PEM-West B) was the large shift in tropical NO levels as a function of geographical location. High-altitude NO levels exceeding 100 pptv were observed during portions of tropical flights 5-8, while values almost never exceeded 20 pptv during tropical flights 9 and 10. The geographical regions encompassing these two flight groupings are here labeled "high" and "low" NOx regimes. A comparison of these two regimes, based on back trajectories and chemical tracers, suggests that air parcels in both were strongly influenced by deep convection. The low NO(x) regime appears to have been predominantly impacted by marine convection, whereas the high NO(x) regime shows evidence of having been more influenced by deep convection over a continental land mass. DMSP satellite observations point strongly toward lightning as the major source of NOx in the latter regime. Photochemical ozone formation in the high NOx regime exceeded that for low NO(x) by factors of 2 to 6, whereas O3 destruction in the low NO(x)regime exceeded that for high NOx by factors of up to 3. Taking the tropopause height to be 17 km, estimates of the net photochemical effect on the O3 column revealed that the high NO(x) regime led to a small net production. By contrast, the low NOx regime was shown to destroy O3 at the rate of 3.4 % per day. One proposed mechanism for off-setting this projected large deficit would involve the transport of 03 rich midlatitude air into the tropics. Alternatively, it is suggested that O3 within the tropics may be overall near self-sustaining with respect to photochemical activity. This scenario would require that some tropical regions, unsampled at the time of PEM-B, display significant net column O3 production, leading to an overall balanced budget for the "greater" tropical Pacific basin. Details concerning the chemical nature of such regimes are discussed.

Crawford, J. H.↗

Measurement of Reactive Nitrogen Compounds over the Tropical Pacific

This report covers the Tropospheric Trace Gas and Airborne Measurement Group's (TTGAMG) participation in the NASA Global Tropospheric Experiment (GTE) Pacific Exploratory Mission: Tropics A (PEM-TA) field measurement program. With other university and NASA centers, the Georgia Institute of Technology Airborne Laser Induced Fluorescence Experiment (GITALIFE) was deployed on the NASA Ames DC-8 aircraft for the measurement of NO and NO2 One of the PEM-TA objectives was to collect the data and interpret the fast photo-chemical processes taking place in the remote and relatively pristine environment over Hawaii, Tahiti, Easter Island, New Zealand, and Fiji.

Sandholm, Scott↗

Measurement of OH, H2SO4, MSA, DMSO, DMSO2 on the NASA P-3B Aircraft

This project involves the deployment of a variety of unique aircraft measurements for the PEM-Tropics program. These measurements were all to be accomplished on a near simultaneous basis using a two channel selected ion chemical ionization mass spectrometer instrument. The first year of this project consisted of four components; improve and perform additional testing of the OH, H2SO4, and MSA instrument which had only flown on one previous mission (ACE-I); develop and test the vacuum and electronic hardware and software which would allow two independent mass spectrometer systems to be operated from a single instrument (one vacuum/pumping system); construct an aircraft compatible DMSO/DMS02 ion source and calibration system; and operate the above system on the NASA P-3B during PEM-Tropics. The first two of the components were to be accomplished at NCAR. The third component was to be completed at Georgia Tech and the fourth was to be conducted by researchers from both institutions on the NASA P-3B.

Eisele, F. L.↗

Simulation of Tropical Biomass Burning

The research objectives that were achieved during the course of our studies include the following: (1) Over the last few years, a model has been developed in the Atmospheric Chemistry and Dynamics Branch at Ames Research Center in collaboration with the Physics Department at San Jose State University. It is referred to as the Global/Regional Atmospheric Chemistry Event Simulator (GRACES). Currently, the GRACES model system combines an atmospheric chemistry and transport model, and a regional mesoscale meteorological model. Therefore this system is suitable for simulating the conditions observed by the tropical observation missions, such as the Pacific Exploratory Mission in the 'Tropics (PEM-Tropics), Study of Ozone and Nitrogen oxides Experiment (SONEX), and other periods. Specifically, the research carried out included the evaluation of the behavior of several components of the MM5 (I.e., Meteorological Model 5, version 2) and the GRACES combined modeling system. We initiated research on (a) the ability of the MM5 model to assimilate downward vertical velocities at least as high as the analyses, (b) the ability of the Graces model to incorporate the vertical velocities from MM5, and (c) other factors related to transport patterns required to transport CO in the observed manner. We carried out improved calculations of the transport of tracers for both NASA airborne missions, SONEX and PEM-Tropics. We also made improved source strength estimates fopr isoprene dust, and similar emissions from the Earths surface. This required the use of newly available databases on the Earth's surface and vegetation. We completed atmospheric chemistry simulations of radicals and nitrogen oxide species. We have greatly improved the handling of cumulonimnbus convection by modifing an existing scheme.

Hamill, Patrick↗

Global Distribution and Sources of Volatile and Nonvolatile Aerosol In the Remote Troposphere

Airborne measurements of aerosol (Condensation Nuclei, CN) and selected trace gases made in the areas of the North Atlantic Ocean during SONEX (October/November 1997), and the south tropical Pacific Ocean during PEM-Tropics A (September/October 1996) and PEM-Tropics B (March/April 1999) have been analyzed. Emphasis is on the interpretations of variations in the number densities of the fine (>17 nm) and ultrafine (>8 nm) CN in the upper troposphere (8-12 km). These data suggest that large number densities of highly volatile CN (10(exp 4)-10(exp 5)/cu cm) are present in the clean upper troposphere with highest values over the tropical1subtropical region. Through marine convection and long-distance horizontal transport, volatile CN originating from the tropical/subtropical regions can frequently impact the abundance of aerosol in the middle and upper troposphere at mid to high latitudes. Nonvolatile aerosol particles behave in a manner similar to tracers of combustion (CO) and photochemical pollution (PAN), implying a source from continental pollution of industrial or biomass burning origin. In the upper troposphere, we find that volatile and nonvolatile partials number densities are inversely correlated. An aerosol microphysical model is used to suggest that coagulation of fine volatile particles with fewer larger nonvolatile particles provides one possible mechanism for this relationship. It appears that nonvolatile particles, of principally anthropogenic origin,provide a highly efficient removal process for the fine volatile aerosol.

Singh, Hanwant B.↗

Overview of the Upper Atmosphere Research Satellite: Observations from 1991 to 2002

The Upper Atmosphere Research Satellite (UARS) was launched in September 1991 by the Space Shuttle Discovery. Seven of the original ten instruments aboard the UARS are functional and six instruments regularly take measurements. The UARS is in a stable observing configuration, in spite of experiencing several anomalies which have impacted the data tape storage and power available. Power sharing and "real-time" operations using the Tracking and Data Relay Satellites have reduced the data collection over the past five years. Although the UARS measurements have not been continuous, the UARS instruments HALOE, SUSIM, SOLSTICE, HRDI, WINDII, and PEM have provided important observations over an entire solar cycle. The UARS HALOE instrument measures ozone and other constituents important in understanding ozone variations. The UARS SUSIM and SOLSTICE instruments observe ultraviolet light between 120 and 420 nm, which influence middle atmospheric constituent fluctuations. The UARS HRDI and WINDII instruments measure winds in the stratosphere, mesosphere, and thermosphere, which move constituents among the various atmospheric regions. The UARS PEM instrument provides observations of input precipitating charged particles, including both electrons and protons. This paper will provide an overview about the UARS mission and its relevant atmospheric measurements.

Jackman, Charles H.↗

Fuel Cell Propulsion Systems for an All-electric Personal Air Vehicle

There is a growing interest in the use of fuel cells as a power source for all-electric aircraft propulsion as a means to substantially reduce or eliminate environmentally harmful emissions. Among the technologies under consideration for these concepts are advanced proton exchange membrane and solid oxide fuel cells, alternative fuels and fuel processing, and fuel storage. This paper summarizes the results of a first-order feasibility study for an all-electric personal air vehicle utilizing a fuel cell-powered propulsion system. A representative aircraft with an internal combustion engine was chosen as a baseline to provide key parameters to the study, including engine power and subsystem mass, fuel storage volume and mass, and aircraft range. The engine, fuel tank, and associated ancillaries were then replaced with a fuel cell subsystem. Various configurations were considered including: a proton exchange membrane (PEM) fuel cell with liquid hydrogen storage; a direct methanol PEM fuel cell; and a direct internal reforming solid oxide fuel cell (SOFC)/turbine hybrid system using liquid methane fuel. Each configuration was compared to the baseline case on a mass and range basis.

Kohout, Lisa L.↗

Fuel Cell Propulsion Systems for an All-Electric Personal Air Vehicle

There is a growing interest in the use of fuel cells as a power source for all-electric aircraft propulsion as a means to substantially reduce or eliminate environmentally harmful emissions. Among the technologies under consideration for these concepts are advanced proton exchange membrane and solid oxide fuel cells, alternative fuels and fuel processing, and fuel storage. This paper summarizes the results of a first-order feasibility study for an all-electric personal air vehicle utilizing a fuel cell-powered propulsion system. A representative aircraft with an internal combustion engine was chosen as a baseline to provide key parameters to the study, including engine power and subsystem mass, fuel storage volume and mass, and aircraft range. The engine, fuel tank, and associated ancillaries were then replaced with a fuel cell subsystem. Various configurations were considered including: a proton exchange membrane (PEM) fuel cell with liquid hydrogen storage; a direct methanol PEM fuel cell; and a direct internal reforming solid oxide fuel cell (SOFC)/turbine hybrid system using liquid methane fuel. Each configuration was compared to the baseline case on a mass and range basis.

Kohout, Lisa L.↗

Lidar Measurements of Relative Humidity and Ice Supersaturation in the Upper Troposphere

We compute upper tropospheric relative humidity profiles using water vapor profiles measured by an airborne DIAL and a ground-based Raman lidar. LASE water vapor and MTP temperature profiles acquired from the NASA DC-8 aircraft during the recent Pacific Exploratory Mission Tropics B (PEM Tropics B) field mission in the tropical Pacific and the SAGE-III Ozone Loss and Validation Experiment (SOLVE) in the Arctic as well as water vapor profiles derived from the ground-based DOE ARM Southern Great Plains (SGP) CART Raman lidar are used. Comparisons of the lidar water vapor measurements with available in situ measurements show reasonable agreement for water vapor mixing ratios above 0.05 g/kg. Relative humidity frequency distributions computed using LASE data indicate that ice supersaturation occurred about 5-11% of the time when temperatures were below -35 C. While a higher frequency of ice supersaturation was observed during SOLVE, higher peak values of relative humidity were observed during PEM Tropics B. The relative humidity fields associated with cirrus clouds are also examined.

Ferrare, Richard A.↗

[Analysis of Multiplatform CO (Carbon Monoxide) Measurements During Trace-P Mission]

Carbon monoxide is considered mission critical (TRACE-P NRA) because it is one of the gases involved in controlling the oxidizing power of the atmosphere and, as a tracer gas, is valuable in interpreting mission data sets. Carbon monoxide exhibits interannual differences, suggesting relatively short-term imbalances in sources and sinks. Sources of CO are dominated by fossil fuel combustion, biomass burning, and the photochemical oxidation of CH4 and nonmethane hydrocarbons while reaction with OH is believed to be the major sink for atmospheric CO, with additional losses due to soil uptake. Uncertainties in the magnitude and distribution of both sources and sinks remain fairly large however, and additional data are required to refine the global budget. Seasonal changes and a northern hemispheric latitudinal gradient have been described for a variety of Pacific basin sites through long-term monitoring of surface background levels. Latitudinal variations have also recently been described at upper tropospheric altitudes over a multi-year period by. TRACE-P will provide an aircraft survey of CO over the northern Pacific in the northern spring when CO concentrations are at their seasonal maximum in the northern hemisphere (NH) and at their seasonal minimum in the southern hemisphere (SH). Previous GTE missions, Le., PEM West-B and PEM Tropics-B, ground-based, and satellite observations (MAPS, April 1994) give us a general picture of the distribution of CO over the northern Pacific during this season. Based on these measurements, background CO levels over remote ocean areas are anticipated to be in the range of 110 - 180 ppbv, while those closer to the Asian continent may rise as high as 600 ppbv. These measurements also reveal high spatial variability (both horizontal and vertical) as well as temporal variations in CO over the area planned for the TRACE-P mission. This variability is a result of multiple CO sources, the meteorological complexity of transport processes, and the photochemical aging of air masses. The influence of biomass burning in the southern Pacific should be relatively small since the mission coincides with the southern tropical wet season when agricultural burning is at its seasonal low. The proposed CO measurements taken during TRACE-P should therefore largely be a function of the impact of various NH sources, primarily Asian and predominantly fossil fuel combustion and biomass burning. These processes are also major sources of many other atmospheric pollutants, consequently making accurate and precise CO measurements is one of the highest TRACE-P priorities [TRACE-P NRA]. The TRACE-P mission emphasizes the dual objectives of assessing the magnitude of the transport of chemically and radiatively important gases such as CO from Asia to the western Pacific, and determining how emissions change and are modified during this transport.

Pougatchev, Nikita S.↗

Electric Power System Technology Options for Lunar Surface Missions

In 2004, the President announced a 'Vision for Space Exploration' that is bold and forward-thinking, yet practical and responsible. The vision explores answers to longstanding questions of importance to science and society and will develop revolutionary technologies and capabilities for the future, while maintaining good stewardship of taxpayer dollars. One crucial technology area enabling all space exploration is electric power systems. In this paper, the author evaluates surface power technology options in order to identify leading candidate technologies that will accomplish lunar design reference mission three (LDRM-3). LDRM-3 mission consists of multiple, 90-day missions to the lunar South Pole with 4-person crews starting in the year 2020. Top-level power requirements included a nominal 50 kW continuous habitat power over a 5-year lifetime with back-up or redundant emergency power provisions and a nominal 2-kW, 2-person unpressurized rover. To help direct NASA's technology investment strategy, this lunar surface power technology evaluation assessed many figures of merit including: current technology readiness levels (TRLs), potential to advance to TRL 6 by 2014, effectiveness of the technology to meet the mission requirements in the specified time, mass, stowed volume, deployed area, complexity, required special ground facilities, safety, reliability/redundancy, strength of industrial base, applicability to other LDRM-3 elements, extensibility to Mars missions, costs, and risks. For the 50-kW habitat module, dozens of nuclear, radioisotope and solar power technologies were down-selected to a nuclear fission heat source with Brayton, Stirling or thermoelectric power conversion options. Preferred energy storage technologies included lithium-ion battery and Proton Exchange Membrane (PEM) Regenerative Fuel Cells (RFC). Several AC and DC power management and distribution architectures and component technologies were defined consistent with the preferred habitat power generation technology option and the overall lunar surface mission. For rover power, more than 20 technology options were down-selected to radioisotope Stirling, liquid lithium-ion battery, PEM RFC, or primary fuel cell options. The author discusses various conclusions that can be drawn from the findings of this surface power technologies evaluation.

Kerslake, Thomas W.↗

Operation of the 25kW NASA Lewis Research Center Solar Regenerative Fuel Cell Tested Facility

Assembly of the NASA Lewis Research Center(LeRC)Solar Regenerative Fuel Cell (RFC) Testbed Facility has been completed and system testing has proceeded. This facility includes the integration of two 25kW photovoltaic solar cell arrays, a 25kW proton exchange membrane (PEM) electrolysis unit, four 5kW PEM fuel cells, high pressure hydrogen and oxygen storage vessels, high purity water storage containers, and computer monitoring, control and data acquisition.

Solar Regenerative Fuel Cell electrolyzer↗

Lunar RFC Reliability Testing for Assured Mission Success

NASA's Constellation program has selected the closed cycle hydrogen oxygen Polymer Electrolyte Membrane (PEM) regenerative Fuel Cell (RFC) as its baseline solar energy storage system for the lunar outpost and manned rover vehicles. Since the outpost and manned rovers are "human-rated", these energy storage systems will have to be of proven reliability exceeding 99 percent over the length of the mission. Because of the low (TRL=5) development state of the closed cycle hydrogen oxygen PEM RFC at present, and because there is no equivalent technology base in the commercial sector from which to draw or infer reliability information from, NASA will have to spend significant resources developing this technology from TRL 5 to TRL 9, and will have to embark upon an ambitious reliability development program to make this technology ready for a manned mission. Because NASA would be the first user of this new technology, NASA will likely have to bear all the costs associated with its development. When well-known reliability estimation techniques are applied to the hydrogen oxygen RFC to determine the amount of testing that will be required to assure RFC unit reliability over life of the mission, the analysis indicates the reliability testing phase by itself will take at least 2 yr, and could take up to 6 yr depending on the number of QA units that are built and tested and the individual unit reliability that is desired. The cost and schedule impacts of reliability development need to be considered in NASA's Exploration Technology Development Program (ETDP) plans, since life cycle testing to build meaningful reliability data is the only way to assure "return to the moon, this time to stay, then on to Mars" mission success.

Bents, David J.↗