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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
NASA NTRS2007

Optical Characterization of Molecular Contaminant Films

A semi-empirical method of optical characterization of thin contaminant films on surfaces of optical components has been conceived. The method was originally intended for application to films that become photochemically deposited on such optical components as science windows, lenses, prisms, thinfilm radiators, and glass solar-cell covers aboard spacecraft and satellites in orbit. The method should also be applicable, with suitable modifications, to thin optical films (whether deposited deliberately or formed as contaminants) on optical components used on Earth in the computer microchip laser communications and thin-film industries. The method is expected to satisfy the need for a means of understanding and predicting the reductions in spectral transmittance caused by contaminant films and the consequent deterioration of performances of sensitive optical systems. After further development, this method could become part of the basis of a method of designing optical systems to minimize or compensate for the deleterious effects of contaminant films. In the original outer-space application, these deleterious effects are especially pronounced because after photochemical deposition, the films become darkened by further exposure to solar vacuum ultraviolet (VUV) radiation. In this method, thin contaminant films are theoretically modeled as thin optical films, characterized by known or assumed values of thickness, index of refraction, and absorption coefficient, that form on the outer surfaces of the original antireflection coating on affected optical components. The assumed values are adjusted as needed to make actual spectral transmittance values approximate observed ones as closely as possible and to correlate these values with amounts of VUV radiation to which the optical components have been exposed. In an initial study, the method was applied in correlating measured changes in transmittance of high-purity fused silica photochemically coated with silicone films of various measured thicknesses and exposed to various measured amounts of VUV radiation. In each case, it was found to be possible to select an index of refraction and absorption coefficient that made the ultraviolet, visible, and infrared transmittance changes predicted by the model match the corresponding measured transmittance changes almost exactly.

Visentine, James T.↗
NASA NTRS2010

Meridional Distribution of CH3C2H and C4H2 in Saturn's Stratosphere from CIRS/Cassini Limb and Nadir Observations

Limb and nadir spectra acquired by Cassini/CIRS (Composite InfraRed Spectrometer) are analyzed in order to derive, for the first time, the meridional variations of diacetylene (C4H2) and methylacetylene (CH3C2H) mixing ratios in Saturn's stratosphere, from 5 hPa up to 0.05 hPa and 80 deg S to 45 deg N. We find that the C4H2 and CH3C2H meridional distributions mimic that of acetylene (C2H2), exhibiting small-scale variations that are not present in photochemical model predictions. The most striking feature of the meridional distribution of both molecules is an asymmetry between mid-southern and mid-northern latitudes. The mid-southern latitudes are found depleted in hydrocarbons relative to their northern counterparts. In contrast, photochemical models predict similar abundances at north and south mid-latitudes. We favor a dynamical explanation for this asymmetry, with upwelling in the south and downwelling in the north, the latter coinciding with the region undergoing ring shadowing. The depletion in hydrocarbons at mid-southern latitudes could also result from chemical reactions with oxygen-bearing molecules. Poleward of 60 deg S, at 0.1 and 0.05 hPa, we find that the CH3C2H and C4H2 abundances increase dramatically. This behavior is in sharp contradiction with photochemical model predictions, which exhibit a strong decrease towards the south pole. Several processes could explain our observations, such as subsidence, a large vertical eddy diffusion coefficient at high altitudes, auroral chemistry that enhances CH3C2H and C4H2 production, or shielding from photolysis by aerosols or molecules produced from auroral chemistry. However, problems remain with all these hypotheses, including the lack of similar behavior at lower altitudes. Our derived mean mixing ratios at 0.5 hPa of (2.4 +/- 0.3) 10(exp -10) for C4H2 and of (1.1 +/- 0.3) 10(exp -9) for CH3C2H are compatible with the analysis of global-average ISO observations performed by Moses et al. Finally, we provide values for the ratios [CH3C2H]/[C2H2] and [C4H2]/[C2H2] that can constrain the coupled chemistry of these hydrocarbons.

Guerlet, Sandrine↗
NASA NTRS2012

Understanding Differences in Upper Stratospheric Ozone Response to Changes in Chlorine and Temperature as Computed Using CCMVal Models

Projections of future ozone levels are made using models that couple a general circulation model with a representation of atmospheric photochemical processes, allowing interactions among photochemical processes, radiation, and dynamics. Such models are known as chemistry and climate models (CCMs). Although developed from common principles and subject to the same boundary conditions, simulated ozone time series vary for projections of changes in ozone depleting substances (ODSs) and greenhouse gases. In the upper stratosphere photochemical processes control ozone level, and ozone increases as ODSs decrease and temperature decreases due to greenhouse gas increase. Simulations agree broadly but there are quantitative differences in the sensitivity of ozone to chlorine and to temperature. We obtain insight into these differences in sensitivity by examining the relationship between the upper stratosphere annual cycle of ozone and temperature as produced by a suite of models. All simulations conform to expectation in that ozone is less sensitive to temperature when chlorine levels are highest because chlorine catalyzed loss is nearly independent of temperature. Differences in sensitivity are traced to differences in simulated temperature, ozone and reactive nitrogen when chlorine levels are close to background. This work shows that differences in the importance of specific processes underlie differences in simulated sensitivity of ozone to composition change. This suggests a) the multi-model mean is not a best estimate of the sensitivity of upper ozone to changes in ODSs and temperature; b) the spread of values is not an appropriate measure of uncertainty.

Douglass, A. R.↗
NASA NTRS2014

Improved Algorithms for Accurate Retrieval of UV - Visible Diffuse Attenuation Coefficients in Optically Complex, Inshore Waters

Photochemical processes driven by high-energy ultraviolet radiation (UVR) in inshore, estuarine, and coastal waters play an important role in global bio geochemical cycles and biological systems. A key to modeling photochemical processes in these optically complex waters is an accurate description of the vertical distribution of UVR in the water column which can be obtained using the diffuse attenuation coefficients of down welling irradiance (Kd()). The Sea UV Sea UVc algorithms (Fichot et al., 2008) can accurately retrieve Kd ( 320, 340, 380,412, 443 and 490 nm) in oceanic and coastal waters using multispectral remote sensing reflectances (Rrs(), Sea WiFS bands). However, SeaUVSeaUVc algorithms are currently not optimized for use in optically complex, inshore waters, where they tend to severely underestimate Kd(). Here, a new training data set of optical properties collected in optically complex, inshore waters was used to re-parameterize the published SeaUVSeaUVc algorithms, resulting in improved Kd() retrievals for turbid, estuarine waters. Although the updated SeaUVSeaUVc algorithms perform best in optically complex waters, the published SeaUVSeaUVc models still perform well in most coastal and oceanic waters. Therefore, we propose a composite set of SeaUVSeaUVc algorithms, optimized for Kd() retrieval in almost all marine systems, ranging from oceanic to inshore waters. The composite algorithm set can retrieve Kd from ocean color with good accuracy across this wide range of water types (e.g., within 13 mean relative error for Kd(340)). A validation step using three independent, in situ data sets indicates that the composite SeaUVSeaUVc can generate accurate Kd values from 320 490 nm using satellite imagery on a global scale. Taking advantage of the inherent benefits of our statistical methods, we pooled the validation data with the training set, obtaining an optimized composite model for estimating Kd() in UV wavelengths for almost all marine waters. This optimized composite set of SeaUVSeaUVc algorithms will provide the optical community with improved ability to quantify the role of solar UV radiation in photochemical and photobiological processes in the ocean.

UV↗
NASA NTRS2018

The Origin of Titan's External Oxygen: Further Constraints from ALMA Upper Limits on CS and CH2NH

Titan's atmospheric inventory of oxygen compounds (H2O, CO2, CO) are thought to result from photochemistry acting on externally supplied oxygen species (O+, OH, H2O). These species potentially originate from two main sources: (1) cryogenic plumes from the active moon Enceladus and (2) micrometeoroid ablation. Enceladus is already suspected to be the major O+ source, which is required for CO creation. However, photochemical models also require H2O and OH influx to reproduce observed quantities of CO2 and H2O. Here, we exploit sulphur as a tracer to investigate the oxygen source because it has very different relative abundances in micrometeorites (S/O approx. 10(exp -2) and Enceladus' plumes (S/O approx. 10(exp -5). Photochemical models predict most sulphur is converted to CS in the upper atmosphere, so we use Atacama Large Millimeter/submillimeter Array (ALMA) observations at approx. 340 GHz to search for CS emission. We determined stringent CS 3 sigma stratospheric upper limits of 0.0074 ppb (uniform above 100 km) and 0.0256 ppb (uniform above 200 km). These upper limits are not quite stringent enough to distinguish between Enceladus and micrometeorite sources at the 3 sigma level and a contribution from micrometeorites cannot be ruled out, especially if external flux is toward the lower end of current estimates. Only the high flux micrometeorite source model of Hickson et al. can be rejected at 3 sigma. We determined a 3 sigma stratospheric upper limit for CH2NH of 0.35 ppb, which suggests cosmic rays may have a smaller influence in the lower stratosphere than predicted by some photochemical models. Disk-averaged C3H4 and C2H5CN profiles were determined and are consistent with previous ALMA and Cassini/CIRS measurements.

Teanby, N.A.↗
NASA NTRS2018

Spatial and Seasonal Variations in C3Hx Hydrocarbon Abundance in Titan's Stratosphere from Cassini CIRS Observations

Of the C3Hx hydrocarbons, propane (C3H8) and propyne (methylacetylene, CH3C2H) were first detected in Titan’s atmosphere during the Voyager 1 flyby in 1980. Propene (propylene, C3H6) was first detected in 2013 with data from the Composite InfraRed Spectrometer (CIRS) instrument on Cassini. We present the first measured abundance profiles of propene on Titan from radiative transfer modeling, and compare our measurements to predictions derived from several photochemical models. Near the equator, propene is observed to have a peak abundance of 10 ppbv at a pressure of 0.2 mbar. Several photochemical models predict the amount at this pressure to be in the range 0.3–1 ppbv and also show a local minimum near 0.2 mbar which we do not see in our measurements. We also see that propene follows a different latitudinal trend than the other C3 molecules. While propane and propyne concentrate near the winter pole, transported via a global convective cell, propene is most abundant above the equator. We retrieve vertical abundances profiles between 125 km and 375 km for these gases for latitude averages between 60°S–20°S, 20°S–20°N, and 20°N–60°N over two time periods, 2004 through 2009 representing Titan’s atmosphere before the 2009 equinox, and 2012 through 2015 representing time after the equinox. Additionally, using newly corrected line data, we determined an updated upper limit for allene (propadiene, CH2CCH2, the isomer of propyne). We claim a 3-σ upper limit mixing ratio of 2.5 × 10(exp −9) within 30° of the equator. The measurements we present will further constrain photochemical models by refining reaction rates and the transport of these gases throughout Titan’s atmosphere.

Lombardo, Nicholas A.↗
NASA NTRS2018

Spatial and Seasonal Variations in C3Hx Hydrocarbon Abundance in Titan’s Stratosphere from Cassini CIRS Observations

Of the C3Hx hydrocarbons, propane (C3H8) and propyne (methylacetylene, CH3C2H) were first detected in Titan’s atmosphere during the Voyager 1 flyby in 1980. Propene (propylene, C3H6) was first detected in 2013 with data from the Composite InfraRed Spectrometer (CIRS) instrument on Cassini. We present the first measured abundance profiles of propene on Titan from radiative transfer modeling, and compare our measurements to predictions derived from several photochemical models. Near the equator, propene is observed to have a peak abundance of 10 ppbv at a pressure of 0.2 mbar. Several photochemical models predict the amount at this pressure to be in the range 0.3 - 1 ppbv and also show a local minimum near 0.2 mbar which we do not see in our measurements. We also see that propene follows a different latitudinal trend than the other C3 molecules. While propane and propyne concentrate near the winter pole, transported via a global convective cell, propene is most abundant above the equator. We retrieve vertical abundances profiles between 125 km and 375 km for these gases for latitude averages between 60◦S to 20◦S, 20◦S to 20◦N, and 20◦N to 60◦N over two time periods, 2004 through 2009 representing Titan’s atmosphere before the 2009 equinox, and 2012 through 2015 representing time after the equinox. Additionally, using newly corrected line data, we determined an updated upper limit for allene (propadiene, CH2CCH2), the isomer of propyne). The measurements we present will further constrain photochemical models, by refining reaction rates and the transport of these gases throughout Titan’s atmosphere.

Nicholas A. Lombardo↗
NASA NTRS2023

Heterogeneity and Chemical Reactivity of the Remote Troposphere Defined By Aircraft Measurements - Corrected

The NASA Atmospheric Tomography (ATom) mission built a photochemical climatology of air parcels based on in situ measurements with the NASA DC-8 aircraft along objectively planned profiling transects through the middle of the Pacific and Atlantic oceans. In this paper we present and analyze a data set of 10 s (2 km) merged and gap-filled observations of the key reactive species driving the chemical budgets of O3 and CH4 (O3, CH4, CO, H2O, HCHO, H2O2, CH3OOH, C2H6, higher alkanes, alkenes, aromatics, NOx, HNO3, HNO4, peroxyacetyl nitrate, and other organic nitrates), consisting of 146 494 distinct air parcels from ATom deployments 1 through 4. Six models calculated the O3 and CH4 photochemical tendencies from this modeling data stream for ATom 1. We find that 80 %–90 % of the total reactivity lies in the top 50 % of the parcels and 25 %–35 % in the top 10 %, supporting previous model-only studies that tropospheric chemistry is driven by a fraction of all the air. Surprisingly, the probability densities of species and reactivities averaged on a model scale (100 km) differ only slightly from the 2 km ATom 10 s data, indicating that much of the heterogeneity in tropospheric chemistry can be captured with current global chemistry models. Comparing the ATom reactivities over the tropical oceans with climatological statistics from six global chemistry models, we find generally good agreement with the reactivity rates for O3 and CH4. Models distinctly underestimate O3 production below 2 km relative to the mid-troposphere, and this can be traced to lower NOx levels than observed. Attaching photochemical reactivities to measurements of chemical species allows for a richer, yet more constrained-to-what-matters, set of metrics for model evaluation.

Tropospheric Chemistry↗
NASA NTRS2016

Limb-Nadir Matching Using Non-Coincident NO2 Observations: Proof of Concept and the OMI-minus-OSIRIS Prototype Product

A variant of the limb-nadir matching technique for deriving tropospheric NO2 columns is presented in which the stratospheric component of the NO2 slant column density (SCD) measured by the Ozone Monitoring Instrument (OMI) is removed using non-coincident profiles from the Optical Spectrograph and InfraRed Imaging System (OSIRIS). In order to correct their mismatch in local time and the diurnal variation of stratospheric NO2, OSIRIS profiles, which were measured just after sunrise, were mapped to the local time of OMI observations using a photochemical boxmodel. Following the profile time adjustment, OSIRIS NO2 stratospheric vertical column densities (VCDs) were calculated. For profiles that did not reach down to the tropopause, VCDs were adjusted using the photochemical model. Using air mass factors from the OMI Standard Product (SP), a new tropospheric NO2 VCD product - referred to as OMI-minus-OSIRIS (OmO) - was generated through limb-nadir matching. To accomplish this, the OMI total SCDs were scaled using correction factors derived from the next-generation SCDs that improve upon the spectral fitting used for the current operational products. One year, 2008, of OmO was generated for 60 deg S to 60 deg N and a cursory evaluation was performed. The OmO product was found to capture the main features of tropospheric NO2, including a background value of about 0.3 x 10(exp 15) molecules per sq cm over the tropical Pacific and values comparable to the OMI operational products over anthropogenic source areas. While additional study is required, these results suggest that a limb-nadir matching approach is feasible for the removal of stratospheric NO2 measured by a polar orbiter from a nadir-viewing instrument in a geostationary orbit such as Tropospheric Emissions: Monitoring of Pollution (TEMPO) or Sentinel-4.

Photochemical Boxmodel↗
NASA NTRS1972

Project Fog Drops. Part 2: Laboratory investigations

Measurements of the total nucleus concentration and cloud condensation nuclei (CCN) were acquired for several conditions representing both high normal and severe pollution levels for the Los Angeles Basin as well as clean filtered air. The data show that in filtered air there is a large photochemically induced increase in the total particle content within a few minutes after starting the lamp. The concentration of CCN remains near zero, until sufficient coagulation and condensation occurs on the smaller Aitken particles. The addition of gaseous pollutants to filtered air results in large increases in the photochemical production of both the cloud and Aitken nucleus concentration. Fogs were also generated under controlled, reproducible conditions in the cloud chamber and seeded with aerosols of various compounds which form monomolecular surface films at air-water interfaces. Visibility characteristics and droplet data were obtained. The data suggest that droplet growth on treated nuclei can be retarded but fog formation was not significantly altered by the chemical seeding.

Kocmond, W. C.↗
NASA NTRS1971

Variable photosynthetic units, energy transfer and light-induced evolution of hydrogen in algae and bacteria.

The present state of knowledge regarding the truly photochemical reactions in photosynthesis is considered. Nine-tenths of the available knowledge is of a biochemical nature. Questions regarding the activities of the chlorophyll system are examined. The simplest photochemical response observed in living hydrogen-adapted algal cells is the release of molecular hydrogen, which continues even after all other known natural reactions have been eliminated either by heating or the action of poisons.

Gaffron, H.↗
NASA NTRS1974

Photolysis of spacecraft contaminants

A molecular beam facility, which was designed to measure photochemical cross-sections, has been constructed at the Athens College science facility. The integration of this vacuum system into an operational photochemical instrument was performed with signal processing consisting of both dc and ac techniques. Of the experiments performed to date on the vacuum ultraviolet photolysis of water vapor, it is apparent that a larger pumping capacity (preferably with differential pumping) is required to improve upon the background signal. Both phase-sensitive detection and ion-counting techniques are recommended for future studies.

Workman, G. L.↗
NASA NTRS1974

Spectroscopy and reactions of molecules important in chemical evolution

The research includes: (1) hot hydrogen atom reactions in terms of the nature of products produced, mechanism of the reactions and the implication and application of such reactions for molecules existing in interstellar clouds, in planetary atmospheres, and in chemical evolution; (2) photochemical reactions that can lead to molecules important in chemical evolution, interstellar clouds and as constituents in planetary atmospheres; and (3) spectroscopic and theoretical properties of biomolecules and their precursors and where possible, use these to understand their photochemical behavior.

Becker, R. S.↗
NASA NTRS1974

Absorption cross sections of stratospheric molecules

Two classes of molecular species must be considered in a calculation of photochemical rates in the stratosphere. The first class consists of molecular oxygen and ozone, while the second class contains the remainder of the minor constituents. If accurate values of the transmitted fluxes are required at large optical depths, the cross sections for molecular oxygen and ozone must be known to within a few per cent at least. On the other hand, the photochemical rates for the minor species are given simply by the relevant cross sections. A review of published cross sections is presented, giving attention to molecular oxygen, ozone, nitric oxide, nitrogen dioxide, nitrous oxide, nitric acid, ammonia, water vapor, hydrogen peroxide, carbon monoxide, carbon dioxide, and sulfur dioxide.

Hudson, R. D.↗
NASA NTRS1975

Infrared spectra of molecules and materials of astrophysical interest

The vibrational spectra from 4000 to 33 cm-1 of several modecules which may be present in the atmosphere of the Jovian planets are studied to provide vibrational frequencies which can be used to: (1) determine the composition of the cloud covers of several of the planets; (2) provide structural information under favorable circumstances; (3) provide necessary data from which accurate thermodynamic data can be calculated; and (4) furnish information as to the nature of the potential energy function of the molecules and forces acting within them. Some of the molecules are produced photochemically from methane, ammonia, and hydrogen sulfide which are thought to be constituents of the planets with reducing atmospheres. Some of the compounds polymerize under ultraviolet radiation and drop out of the atmospheres. However, planets with a hot base, like that of Jupiter, may rebuild molecules destroyed photochemically.

Durig, J. R.↗
NASA NTRS1975

Venus - Chemical and dynamical processes in the stratosphere and mesosphere

Photochemical models for the Venus clouds are presented and discussed. We illustrate models for sulfuric acid density as a function of altitude based on a proposed photochemical scheme. Emphasis is placed on two competing removal mechanisms for sulfur atoms above the visible clouds: S + O2 yields SO + O, and S + COS yields S2 + CO. The first reaction (which forms the major oxygen sink in the visible cloud region) requires reasonable O2 concentrations and leads to sulfuric acid production. The second reaction occurs in regions where O2 is severely depleted and leads to elemental sulfur production. Quantitative estimates of the balance between these two competing processes are presented together with a discussion of the complete sulfur and oxygen cycles on the planet. We propose that the dark regions in the ultraviolet of Venus are oxygen-depleted regions where a significant amount of ultraviolet-absorbing sulfur is being produced. We also discuss observations of particle densities on Venus and their implications for vertical mixing rates.

Prinn, R. G.↗
NASA NTRS1976

Infrared spectra of molecules and materials of astrophysical interest

The vibrational spectra from 4,000 to 33/cm of several molecules which may be present in the atmosphere of the Jovian planets or exist in outer space were studied. These studies have been made to provide vibrational frequencies which can be used to: (1) determine the composition of the cloud covers of several of the planets, (2) provide structural information under favorable circumstances, (3) provide necessary data from which accurate thermodynamic data can be calculated, and (4) furnish information as to the nature of the potential energy function of the molecules and forces acting within them. Some of the molecules studied can be produced photochemically from methane, ammonia, and hydrogen sulfide which are thought to be constituents of the planets with reducing atmospheres. Some of the compounds will polymerize under ultraviolet radiation and drop out of the atmospheres. However, planets with a hot base, like that of Jupiter, may rebuild molecules destroyed photochemically. These criteria were used in selecting the compounds under study.

Durig, J. R.↗
NASA NTRS1977

The structure of cometary ionospheres. II - CO-rich comets

The structure of the ionosphere of a CO-rich comet is computed using two different models. The first one, the photochemical model, assumes that the dissociation and ionization of cometary neutrals and ions are due to photoionization, and photodissociation by solar UV radiation together with dissociative recombinations and ion-neutral reactions. The second one, the internal source model, also incorporates the ionization and dissociation effects of an electric current discharging through the inner coma. The generation of this current has been discussed in earlier papers. It is concluded that the internal source model can explain qualitatively the basic morphology of the ionospheres of CO-rich comets such as Humason (1962, VIII) and Morehouse (1908, III), whereas the photochemical model cannot. The main aim of this paper is not so much to provide accurate numerical estimates as to draw attention to a process which may very well dominate the structures of cometary ionospheres.

Ip, W.-H.↗