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[Global Atmospheric Chemistry/Transport Modeling and Data-Analysis]

This grant supported a global atmospheric chemistry/transport modeling and data- analysis project devoted to: (a) development, testing, and refining of inverse methods for determining regional and global transient source and sink strengths for trace gases; (b) utilization of these inverse methods which use either the Model for Atmospheric Chemistry and Transport (MATCH) which is based on analyzed observed winds or back- trajectories calculated from these same winds for determining regional and global source and sink strengths for long-lived trace gases important in ozone depletion and the greenhouse effect; (c) determination of global (and perhaps regional) average hydroxyl radical concentrations using inverse methods with multiple "titrating" gases; and (d) computation of the lifetimes and spatially resolved destruction rates of trace gases using 3D models. Important ultimate goals included determination of regional source strengths of important biogenic/anthropogenic trace gases and also of halocarbons restricted by the Montreal Protocol and its follow-on agreements, and hydrohalocarbons now used as alternatives to the above restricted halocarbons.

Prinn, Ronald G.↗

Ultrasensitive Human Radiation Dosimetry

The problem we are addressing concerns the astronauts, and their exposure to radiation during spaceflight. The amount of this radiation is a variable depending on solar events and orbital characteristics. Our goal is to measure the total integrated quantity of radiation damage to the cell nucleus in astronauts or other people exposed to radiation. In my lab, we are turning up the microscope from the level of the chromosome, about eight orders of magnitude, to the molecular level. It is well known that radiation causes DNA and chromosome damage. We are developing methods to measure a specific molecular lesion. The lesion that we have selected to measure is thymidine diol, which is created by hydroxyl radicals adding across the 5.6 double bond of thymidine in DNA.

Hammen, Richard↗

The Distribution of Carbon Monoxide in the GOCART Model

Carbon monoxide (CO) is an important trace gas because it is a significant source of tropospheric Ozone (O3) as well as a major sink for atmospheric hydroxyl radical (OH). The distribution of CO is set by a balance between the emissions, transport, and chemical processes in the atmosphere. The Georgia Tech/Goddard Global Ozone Chemistry Aerosol Radiation and Transport (GOCART) model is used to simulate the atmospheric distribution of CO. The GOCART model is driven by the assimilated meteorological data from the Goddard Earth Observing System Data Assimilation System (GEOS DAS) in an off-line mode. We study the distribution of CO on three time scales: (1) day to day fluctuation produced by the synoptic waves; (2) seasonal changes due to the annual cycle of CO sources and sinks; and (3) interannual variability induced by dynamics. Comparison of model results with ground based and remote sensing measurements will also be presented.

Fan, Xiaobiao↗

Methanogenesis, Mesospheric Clouds, and Global Habitability

Hyperthermophilic methanogens can exist in a deep hot biosphere up to 110 C, or 10 km deep. Methane (CH4) itself is thermodynamically stable to depths of 300 km. Geologic (microbial plus abiogenic thermal) methane is transported upward, attested to by its association with helium, to form petroleum pools. Near or at the surface, geologic CH4 mixes with other natural and with anthropogenic CH4 yielding annual emissions into the atmosphere of 500 Tg, of which 200 Tg are natural and 300 Tg are man-made. The atmospheric lifetime of CH4, a greenhouse gas 20 times more effective than CO2 in raising global temperatures, is approximately 10 years. It is removed from the atmosphere mainly by reactions with hydroxyl radical (OH) to form CO2, but also by dry soil and by conversion to H2O in the stratosphere and middle atmosphere. A sudden rise in atmospheric temperatures by 9-12 C some 55 million years ago has been explained by the release in a few thousand years of three trillion tons of CH4 out of 15 trillion tons that had formed beneath the sea floor. What prevented this CH4-induced greenhouse effect from running away? An analog to the CH4-burp of 55 million years ago is the CH4-doubling over the past century which resulted in a increase in upper level H2O from 4.3 ppmv to 6 ppmv. This 30% increase in H2O vapor yielded a tenfold increase in brightness of polar mesospheric clouds because of a strong dependence of the ice particle nucleation rate on the water saturation ratios. Models show that at a given temperature the optical depth of mesospheric clouds scales as [H2O]beta with beta varying between 4 and 8. Radiative transfer tools applied to mesospheric particles suggest that an optical depth of approximately one, or 1000 times the current mesospheric cloud optical depth, would result in tropospheric cooling of about 10 K. Assuming beta=6, a thousandfold increase in optical thickness would require a three-fold increase of H2O, or a 20-fold increase of CH4. At the current rate of anthropogenic emissions this is expected to occur within the next 1000 years. This timescale is also commensurate with what has been assumed for the CH4- burp 55 million years ago.

Pueschel, Rudolf F.↗

Global Ozone and Reactive Nitrogen : Composition, Chemistry and Sources

Ozone plays a central role in the chemistry of the atmosphere both as an ultraviolet shield and as a source of hydroxyl radicals (OH), a potent initiator of atmospheric chemistry. There is evidence to suggest that the ozone abundance in the troposphere (0-10 km) has doubled since the industrial revolution and continues to increase to date. The principle reason for this increase is thought to be the increasing emissions of nitrogen oxides (NO(x)) from anthropogenic activities. Although NO(x) is highly reactive and its products such as HN03 are easily removed by deposition, it now appears that its chemistry is quite complex and it can be transported over long distances via its conversion to a variety of nitrates and penetrates. The sources of atmospheric NO(x) include free tropospheric sources such as lightning and subsonic aircraft, as well as surface emissions which are transported to the free troposphere via convective processes. Recent experimental and theoretical studies have tried to unravel the chemistry of reactive nitrogen species, its sources, and their role in ozone formation. In this presentation we shall describe the results from these studies.

Sing, Hanwant B.↗

Sulfuric Acid and Soot Particles in Aircraft Exhaust

Aircraft have become the fastest, fairly convenient and, in most cases of long-distance travel, most economical mode of travel. This is reflected in the increase of commercial air traffic at a rate of 6% per year since 1978. Future annual growth rates of passenger miles of 4% for domestic and 6% for international routes are projected. A still larger annual increase of 8.5% is expected for the Asia/Pacific region. To meet that growth, Boeing predicts the addition of 15,900 new aircraft to the world's fleets, valued at more than $1.1 trillion, within the next 20 years. The largest concern of environmental consequences of aircraft emissions deals with ozone (O3), because: (1) the O3 layer protects the blaspheme from short-ultraviolet radiation that can cause damage to human, animal and plant life, and possibly affect agricultural production and the marine food chain; (2) O3 is important for the production of the hydroxyl radical (OH) which, in turn, is responsible for the destruction of other greenhouse gases, e.g., methane (CH4) and for the removal of other pollutants, and (3) O3 is a greenhouse gas. Additional information is contained in the original extended abstract.

Pueschel, Rudolf F.↗

Studies of Trace Gas Chemical Cycles Using Inverse Methods and Global Chemical Transport Models

We report progress in the first year, and summarize proposed work for the second year of the three-year dynamical-chemical modeling project devoted to: (a) development, testing, and refining of inverse methods for determining regional and global transient source and sink strengths for long lived gases important in ozone depletion and climate forcing, (b) utilization of inverse methods to determine these source/sink strengths using either MATCH (Model for Atmospheric Transport and Chemistry) which is based on analyzed observed wind fields or back-trajectories computed from these wind fields, (c) determination of global (and perhaps regional) average hydroxyl radical concentrations using inverse methods with multiple titrating gases, and (d) computation of the lifetimes and spatially resolved destruction rates of trace gases using 3D models. Important goals include determination of regional source strengths of methane, nitrous oxide, methyl bromide, and other climatically and chemically important biogenic/anthropogenic trace gases and also of halocarbons restricted by the Montreal protocol and its follow-on agreements and hydrohalocarbons now used as alternatives to the restricted halocarbons.

Prinn, Ronald G.↗

Biomass Burning and the Production of Greenhouse Gases

Biomass burning is a source of greenhouse gases, carbon dioxide, methane, and nitrous oxide. In addition, biomass burning is a source of chemically active gases, including carbon monoxide, nonmethane hydrocarbons, and nitric oxide. These gases, along with methane, lead to the chemical production of tropospheric ozone (another greenhouse gas) as well as control the concentration of the hydroxyl radical, which regulates the lifetime of almost every atmospheric gas. Following biomass burning, biogenic emissions of nitrous oxide, nitric oxide, and methane are significantly enhanced. It is hypothesized that enhanced postburn biogenic emissions of these gases are related to fire-induced changes in soil chemistry and/or microbial ecology. Biomass burning, once believed to be a tropical phenomenon, has been demonstrated by satellite imagery to also be a regular feature of the world's boreal forests. One example of biomass burning is the extensive 1987 fire that destroyed more than 12 million acres of boreal forest in the People's Republic of China and across its border in the Soviet Union. Recent estimates indicate that almost all biomass burning is human-initiated and that it is increasing with time. With the formation of greenhouse and chemically active gases as direct combustion products and a longer-term enhancement of biogenic emissions of gases, biomass burning may be a significant driver for global change.

Levine, Joel S.↗

Droplet Combustion Experiment

Liquid fuel combustion provides a major portion of the world's energy supply. In most practical combustion devices, liquid burns after being separated into a droplet spray. Essential to the design of efficient combustion systems is a knowledge of droplet combustion behavior. The microgravity environment aboard spacecraft provides an opportunity to investigate the complex interactions between the physical and chemical combustion processes involved in droplet combustion without the complications of natural buoyancy. Launched on STS-83 and STS-94 (April 4 and July 1, 1997), the Droplet Combustion Experiment (DCE) investigated the fundamentals of droplet combustion under a range of pressures (0.25 to 1 atm), oxygen mole fractions (<0.5), and droplet sizes (1.5 to 5 mm). Principal DCE flight hardware features were a chamber to supply selected test environments, the use of crew-inserted bottles, and a vent system to remove unwanted gaseous combustion products. The internal apparatus contained the droplet deployment and ignition mechanisms to burn single, freely deployed droplets in microgravity. Diagnostics systems included a 35-mm high-speed motion picture camera (see the following sequence of photos) with a backlight to photograph burning droplets and a camcorder to monitor experiment operations. Additional diagnostics included an ultraviolet-light-sensitive CCD (charge couple discharge) camera to obtain flame radiation from hydroxyl radicals (see the final figure) and a 35-mm SLR (single-lens-reflex) camera to obtain color still photographs of the flames.

Nayagam, Vedha↗

Modeling of Radiation Risks for Human Space Missions

Prior to any human space flight, calculations of radiation risks are used to determine the acceptable scope of astronaut activity. Using the supercomputing facilities at NASA Ames Research Center, Ames researchers have determined the damage probabilities of DNA functional groups by space radiation. The data supercede those used in the current Monte Carlo model for risk assessment. One example is the reaction of DNA with hydroxyl radical produced by the interaction of highly energetic particles from space radiation with water molecules in the human body. This reaction is considered an important cause of DNA mutations, although its mechanism is not well understood.

Fletcher, Graham↗

Optical Diagnosis of Gas Turbine Combustors Being Conducted

Researchers at the NASA Glenn Research Center, in collaboration with industry, are reducing gas turbine engine emissions by studying visually the air-fuel interactions and combustion processes in combustors. This is especially critical for next generation engines that, in order to be more fuel-efficient, operate at higher temperatures and pressures than the current fleet engines. Optically based experiments were conducted in support of the Ultra-Efficient Engine Technology program in Glenn's unique, world-class, advanced subsonic combustion rig (ASCR) facility. The ASCR can supply air and jet fuel at the flow rates, temperatures, and pressures that simulate the conditions expected in the combustors of high-performance, civilian aircraft engines. In addition, this facility is large enough to support true sectors ("pie" slices of a full annular combustor). Sectors enable one to test true shapes rather than rectangular approximations of the actual hardware. Therefore, there is no compromise to actual engine geometry. A schematic drawing of the sector test stand is shown. The test hardware is mounted just upstream of the instrumentation section. The test stand can accommodate hardware up to 0.76-m diameter by 1.2-m long; thus sectors or small full annular combustors can be examined in this facility. Planar (two-dimensional) imaging using laser-induced fluorescence and Mie scattering, chemiluminescence, and video imagery were obtained for a variety of engine cycle conditions. The hardware tested was a double annular sector (two adjacent fuel injectors aligned radially) representing approximately 15 of a full annular combustor. An example of the two-dimensional data obtained for this configuration is also shown. The fluorescence data show the location of fuel and hydroxyl radical (OH) along the centerline of the fuel injectors. The chemiluminescence data show C2 within the total observable volume. The top row of this figure shows images obtained at an engine low-power condition, and the bottom row shows data from a higher power operating point. The data show distinctly the differences in flame structure between low-power and high-power engine conditions, in both location and amount of species produced (OH, C2) or consumed (fuel). The unique capability of the facility coupled with its optical accessibility helps to eliminate the need for high-pressure performance extrapolations. Tests such as described here have been used successfully to assess the performance of fuel-injection concepts and to modify those designs, if needed.

Hicks, Yolanda R.↗

Sensitivity of Photolysis Frequencies and Key Tropospheric Oxidants in a Global Model to Cloud Vertical Distributions and Optical Properties

As a follow-up study to our recent assessment of the radiative effects of clouds on tropospheric chemistry, this paper presents an analysis of the sensitivity of such effects to cloud vertical distributions and optical properties in a global 3-D chemical transport model (GEOS4-Chem CTM). GEOS-Chem was driven with a series of meteorological archives (GEOS1-STRAT, GEOS-3 and GEOS-4) generated by the NASA Goddard Earth Observing System data assimilation system, which have significantly different cloud optical depths (CODs) and vertical distributions. Clouds in GEOS1-STRAT and GEOS-3 have more similar vertical distributions while those in GEOS-4 are optically much thinner in the tropical upper troposphere. We find that the radiative impact of clouds on global photolysis frequencies and hydroxyl radical (OH) is more sensitive to the vertical distribution of clouds than to the magnitude of column CODs. Model simulations with each of the three cloud distributions all show that the change in the global burden of O3 due to clouds is less than 5%. Model perturbation experiments with GEOS-3, where the magnitude of 3-D CODs are progressively varied by -100% to 100%, predict only modest changes (<5%) in global mean OH concentrations. J(O1D), J(NO2) and OH concentrations show the strongest sensitivity for small CODs and become insensitive at large CODs due to saturation effects. Caution should be exercised not to use in photochemical models a value for cloud single scattering albedo lower than about 0.999 in order to be consistent with the current knowledge of cloud absorption at the UV wavelength. Our results have important implications for model intercomparisons and climate feedback on tropospheric photochemistry.

Liu, Hongyu↗

Understanding the Activation and Solution Properties of Lunar Dust for Future Lunar Habitation

The decision to return humans to the moon by 2020 makes it imperative to understand the effects of lunar dust on human and mechanical systems.( Bush 2004; Gaier 2005; Mendell 2005) During the Apollo missions, dust was found to cause numerous problems for various instruments and systems. Additionally, the dust may have caused health issues for some of the astronauts.(Gaier 2005; Rowe 2007) It is necessary, therefore, for studies to be carried out in a variety of disciplines in order to mitigate the effects of the dust as completely as possible. Due to the lack of an atmosphere, there is nothing to protect the lunar soil from ultraviolet radiation, solar wind, and meteorite impacts. These processes could all serve to "activate" the soil, or produce reactive surface species. In order to understand the possible toxic effects of the reactive dust, it is necessary to "reactivate" the dust, as samples returned during the Apollo missions were exposed to the atmosphere of the Earth. We have used grinding and exposure to UV radiation in order to mimic some of the processes occurring on the lunar surface. To monitor the reactivity of the dust, we have measured the ability of the dust to produce hydroxyl radicals in solution. These radicals have been measured using a novel fluorescent technique developed in our laboratory,(Wallace et al. 2008) as well as using electron paramagnetic resonance (EPR).

Wallace, William T.↗

Understanding the Potential Toxic Properties of Lunar Dust

Lunar dust causes a variety of problems for spacecraft. It can obscure vision, clog equipment, cause seal failures and abrade surfaces. Additionally, lunar dust is potentially toxic and therefore hazardous to astronauts. Lunar dust can be activated by meteorites, UV radiation and elements of solar wind and, if inhaled, could produce reactive species in the lungs (freshly fractured quartz). Methods of lunar dust deactivation must be determined before new lunar missions. This requires knowledge of how to reactivate lunar dust on Earth - thus far crushing/grinding, UV activation and heating have been tested as activation methods. Grinding of lunar dust leads to the production of hydroxyl radicals in solution and increased dissolution of lunar simulant in buffers of different pH. Decreases in pH lead to increased lunar simulant leaching. Additionally, both ground and unground lunar simulant and unground quartz have been shown to promote the production of IL-6 and IL-8, pro-inflammatory cytokines, by alveolar epithelial cells. The results suggest the need for further studies on lunar dust and simulants prior to returning to the lunar surface.

Source record↗

Chemically Assisted Photocatalytic Oxidation System

The chemically assisted photocatalytic oxidation system (CAPOS) has been proposed for destroying microorganisms and organic chemicals that may be suspended in the air or present on surfaces of an air-handling system that ventilates an indoor environment. The CAPOS would comprise an upstream and a downstream stage that would implement a tandem combination of two partly redundant treatments. In the upstream stage, the air stream and, optionally, surfaces of the air-handling system would be treated with ozone, which would be generated from oxygen in the air by means of an electrical discharge or ultraviolet light. In the second stage, the air laden with ozone and oxidation products from the first stage would be made to flow in contact with a silica-titania photocatalyst exposed to ultraviolet light in the presence of water vapor. Hydroxyl radicals generated by the photocatalytic action would react with both carbon containing chemicals and microorganisms to eventually produce water and carbon dioxide, and ozone from the first stage would be photocatalytically degraded to O2. The net products of the two-stage treatment would be H2O, CO2, and O2.

Andino, Jean↗

Photocatalytic Coatings for Exploration and Spaceport Design

This project developed self-cleaning photocatalytic coatings that remove contamination without human intervention. The coatings chemically remove organic contaminants and leave no residue. The photocatalyst will not negatively affect other coating properties, especially corrosion resistance. Titanium dioxide, TiO2, is an extremely popular photocatalyst because of its chemical stability, nontoxicity, and low cost. TiO2 is commonly used in the photocatalytic oxidation of organic matter or pollutants in the gas and liquid phases. However, TiO2 does have some drawbacks. It has limited light absorption because of its large band-gap and suffers from a photonic efficiency of less than 10 percent for organic degradation. Dopants can lower the band-gap and improve efficiency. Since the photocatalytically active form of TiO2 is a nanocrystalline powder, it can be difficult to make a robust coating with enough catalyst loading to be effective. Photocatalysts become active when certain light energy is absorbed. When photons with an energy greater than the band-gap, Eg, (wavelengths shorter than 400 nm) impinge upon the surface of the TiO2, an electron-hole pair is formed. The electron-hole pair oxidizes adsorbed substances either directly or via reactive intermediates that form on the surface, such as hydroxyl radicals (OH) or superoxide ions (O2-). Several factors can influence the band-gap energy of TiO2, two of which are crystal structure and impurities. TiO2 exists as three crystal structures brookite, anatase, and rutile that can be controlled via heat treatment. Anatase is the most photocatalytically active crystal form of TiO2. Doping TiO2 with impurities can alter its band-gap energy, as well as its effectiveness as a catalyst. Depending on their size, dopant atoms can occupy either the substitutional or interstitial lattice positions. Atoms that are relatively large will assume the interstitial positions and create a much greater energy disturbance in the crystal than will smaller atoms that take on the substitutional positions. This energy disturbance narrows the band-gap and thus allows photons with longer wavelengths and smaller energies (such as those in the visible-light spectrum) to create electron-hole pairs. Raman spectroscopy was performed for the purpose of determining the crystal structure and the degree of crystallinity of the TiO2 particles. Reflectance measurements indicated the wavelengths of light absorbed by the different catalysts.

Source record↗

Sensitivity of Photolysis Frequencies and Key Tropospheric Oxidants in a Global Model to Cloud Vertical Distributions and Optical Properties

Clouds affect tropospheric photochemistry through modification of solar radiation that determines photolysis frequencies. As a follow-up study to our recent assessment of the radiative effects of clouds on tropospheric chemistry, this paper presents an analysis of the sensitivity of such effects to cloud vertical distributions and optical properties (cloud optical depths (CODs) and cloud single scattering albedo), in a global 3-D chemical transport model (GEOS-Chem). GEOS-Chem was driven with a series of meteorological archives (GEOS1- STRAT, GEOS-3 and GEOS-4) generated by the NASA Goddard Earth Observing System data assimilation system. Clouds in GEOS1-STRAT and GEOS-3 have more similar vertical distributions (with substantially smaller CODs in GEOS1-STRAT) while those in GEOS-4 are optically much thinner in the tropical upper troposphere. We find that the radiative impact of clouds on global photolysis frequencies and hydroxyl radical (OH) is more sensitive to the vertical distribution of clouds than to the magnitude of column CODs. With random vertical overlap for clouds, the model calculated changes in global mean OH (J(O1D), J(NO2)) due to the radiative effects of clouds in June are about 0.0% (0.4%, 0.9%), 0.8% (1.7%, 3.1%), and 7.3% (4.1%, 6.0%), for GEOS1-STRAT, GEOS-3 and GEOS-4, respectively; the geographic distributions of these quantities show much larger changes, with maximum decrease in OH concentrations of approx.15-35% near the midlatitude surface. The much larger global impact of clouds in GEOS-4 reflects the fact that more solar radiation is able to penetrate through the optically thin upper-tropospheric clouds, increasing backscattering from low-level clouds. Model simulations with each of the three cloud distributions all show that the change in the global burden of ozone due to clouds is less than 5%. Model perturbation experiments with GEOS-3, where the magnitude of 3-D CODs are progressively varied from -100% to 100%, predict only modest changes (<5%) in global mean OH concentrations. J(O1D), J(NO2) and OH3 concentrations show the strongest sensitivity for small CODs and become insensitive at large CODs due to saturation effects. Caution should be exercised not to use in photochemical models a value for cloud single scattering albedo lower than about 0.999 in order to be consistent with the current knowledge of cloud absorption at the ultraviolet wavelengths.

Liu, Hongyu↗

Partitioning the LIS/OTD Lightning Climatological Dataset into Separate Ground and Cloud Flash Distributions

Presently, it is not well understood how to best model nitrogen oxides (NOx) emissions from lightning because lightning is highly variable. Peak current, channel length, channel altitude, stroke multiplicity, and the number of flashes that occur in a particular region (i.e., flash density) all influence the amount of lightning NOx produced. Moreover, these 5 variables are not the same for ground and cloud flashes; e.g., cloud flashes normally have lower peak currents, higher altitudes, and higher flash densities than ground flashes [see (Koshak, 2009) for additional details]. Because the existing satellite observations of lightning (Fig. 1) from the Lightning Imaging Sensor/Optical Transient Detector (LIS/OTD) do not distinguish between ground and cloud fashes, which produce different amounts of NOx, it is very difficult to accurately account for the regional/global production of lightning NOx. Hence, the ability to partition the LIS/OTD lightning climatology into separate ground and cloud flash distributions would substantially benefit the atmospheric chemistry modeling community. NOx indirectly influences climate because it controls the concentration of ozone and hydroxyl radicals in the atmosphere. The importance of lightning-produced NOx is empasized throughout the scientific literature (see for example, Huntrieser et al. 1998). In fact, lightning is the most important NOx source in the upper troposphere with a global production rate estimated to vary between 2 and 20 Tg (N)yr(sup -1) (Lee et al., 1997), with more recent estimates of about 6 Tg(N)yr(sup -1) (Martin et al., 2007). In order to make accurate predictions, global chemistry/climate models (as well as regional air quality modells) must more accurately account for the effects of lightning NOx. In particular, the NASA Goddard Institute for Space Studies (GISS) Model E (Schmidt et al., 2005) and the GEOS-CHEM global chemical transport model (Bey et al., 2001) would each benefit from a partitioning of the LIS/OTD lightning climatology. In this study, we introduce a new technique for retrieving the ground flash fraction in a set of N lightning observed from space and that occur within a specific latitude/longitude bin. The method is briefly described and applied to CONUS lightning that have already been partitioned into ground and cloud flashes using independent ground-based observations, in order to assess the accuracy of the retrieval method. The retrieval errors are encouragingly small.

Koshak, W. J.↗