Search NASA⌕ Search

SEARCH · Search NASA

Results for “Photochemical”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
NASA NTRS1996

Monitoring the Photosynthetic Apparatus During Space Flight: Interspecific Variation in Chlorophyll Fluorescence Signatures Induced by Different Root Zone Stresses

Chlorophyll fluorescence has been used extensively as a tool to indicate stress to the photosynthetic apparatus in green plants. A rise in fluorescence has been attributed to the blockage of photosystem II photochemistry, and patterns of fluorescence decay (quenching) from dark adapted leaves can be related to specific photochemical and non-photochemical deexcitation pathways of light trapped by the photosynthetic apparatus and thus result in characteristically different fluorescence signatures. Four distantly related plant species, Hypocharis radicata (Asteraceae), Brassica rapa (Brassicaceae), Spinacea oleracea (Chenopodiaceae) and Triticum aestivum (Poaceae), were grown hydroponically for three weeks before the initiation of three different root zone stresses (10 mM Cu, 100 mM NaCl and nitrogen deficient nutrition). After 10 days, characteristic fluorescence signatures for each stress could be noted although the degree varied between species. Fast kinetics analysis showed a reduction in plastoquinone pool size for copper and nitrogen stress for all species but a more species specific result with NaCl stress. Photochemical quenching kinetics varied between species and stress treatments from no quenching in S. oleracea in copper treatments to increased photochemical quenching in NaCl treatments. Non-photochemical quenching kinetics demonstrated a distinct pattern between stresses for all species. Copper treatments characteristically exhibited a shallow, flat non-photochemical quenching profile suggesting a general blockage of electron transport whereas NaCl treatments exhibited a slow rising profile that suggested damage to thylakoid acidification kinetics and nitrogen deficiency exhibited a fast rising and declining profile that suggested an altered state 1-state 2 transition regulated by the phosphorylation of LHCII. These results demonstrate characteristic fluorescence signatures for specific plant stresses that may be applied to different, unrelated plant species. In addition, the potential use of chlorophyll fluorescence for both basic research and diagnostic physiology in space biology is presented.

Bubenheim, David L.↗
NASA NTRS1991

Method for determining stable isotope ratios of dissolved organic carbon in interstitial and other natural marine waters

A procedure is described for the analysis of the stable carbon isotopic composition of dissolved organic carbon (DOC) in natural waters from marine and higher-salinity environments. Rapid (less than 5 min) and complete oxidation of DOC is achieved using a modification of previous photochemical oxidation techniques. The CO2 evolved from DOC oxidation can be collected in less than 10 min for isotopic analysis. The procedure is at present suitable for oxidation and collection of 1-5 micromoles of carbon and has an associated blank of 0.1-0.2 micromole of carbon. Complete photochemical oxidation of DOC standards was demonstrated by quantitative recovery of CO2 as measured manometrically. Isotopic analyses of standards by photochemical and high-temperature sealed-tube combustion methods agreed to within 0.3%. Photochemical oxidation of DOC in a representative sediment pore-water sample was also quantitative, as shown by the excellent agreement between the photochemical and sealed-tube methods. The delta 13C values obtained for pore-water DOC using the two methods of oxidation were identical, suggesting that the modified photochemical method is adequate for the isotopically non-fractionated oxidation of pore-water DOC. The procedure was evaluated through an analysis of DOC in pond and pore waters from a hypersaline microbial mat environment. Concentrations of DOC in the water column over the mat displayed a diel pattern, but the isotopic composition of this DOC remained relatively constant (average delta 13C = -12.4%). Pore-water DOC exhibited a distinct concentration maximum in the mat surface layer, and delta 13C of pore-water DOC was nearly 8% lighter at 1.5-2.0-cm depth than in the mat surface layer (0-0.5-cm depth). These results demonstrate the effectiveness of the method in elucidating differences in DOC concentration and delta 13C over biogeochemically relevant spatial and temporal scales. Carbon isotopic analysis of DOC in natural waters, especially pore waters, should be a useful probe of biogeochemical processes in recent environments.

NASA Discipline Exobiology↗
NASA NTRS2011

Sulfur Chemistry in the Early and Present Atmosphere of Mars

Atmospheric sulfur species resulting from volcanic emissions impact the composition and chemistry of the atmosphere, impact the climate, and hence, the habitability of Mars and impact the mineralogy and composition of the surface of Mars. The geochemical/ photochemical cycling of sulfur species between the interior (via volcanism), the atmosphere (atmospheric photochemical and chemical processes) and the deposition of sulfuric acid on the surface of Mars is an important, but as yet poorly understood geochemical/ photochemical cycle on Mars. There is no observational evidence to indicate that Mars is volcanically active at the present time, however, there is strong evidence that volcanism was an important and widespread process on early Mars. The chemistry and photochemistry of sulfur species in the early and present atmosphere of Mars will be assessed using a one-dimensional photochemical model. Since it is generally assumed that the atmosphere of early Mars was significantly denser than the present 6-millibar atmosphere, photochemical calculations were performed for the present atmosphere and for the atmosphere of early Mars with assumed surface pressures of 60 and 350-millibars, where higher surface pressure resulted from enhanced atmospheric concentrations of carbon dioxide (CO2). The following sections include the results of earlier modeling studies, a summary of the one-dimensional photochemical model used in this study, a summary of the photochemistry and chemistry of sulfur species in the atmosphere of Mars and some of the results of the calculations.

Levine, Joel S.↗
NASA NTRS1977

Photochemistry of tropospheric ozone

A photochemical equilibrium model of minor constituent chemistry in the troposphere was constructed to investigate the photochemistry of tropospheric ozone. We find that photochemical production must be supplemented by additional sources to account for observed ozone levels in clean air, while photochemical loss is more important than surface destruction as an ozone loss mechanism. Photochemically produced ozone is sensitive to the NO(x) background in the model, exhibiting a maximum of about 0.5 ppb of NO(x).

Stewart, R. W.↗
NASA NTRS1981

Observations of the interaction of ozone and dynamics

Data on the global distribution of temperature and ozone obtained with the Limb Radiance Inversion Radiometer which flew on the Nimbus 6 spacecraft are analyzed within the conceptual framework of Hartmann and Garcia (1979). The analysis supports the conclusion that ozone perturbations are dynamically controlled when the photochemical time constant is much greater than the dynamical time constant; when the photochemical constant is much less than the dynamical constant, ozone perturbations are photochemically controlled. It is also shown that the transports of planetary waves, or eddy transports, appear to be strongly localized in the region between the regimes in which dynamical and photochemical controls operate.

Gille, J. C.↗
NASA NTRS1986

The production of trace gases by photochemistry and lightning in the early atmosphere

Recent atmospheric calculation suggest that the prebiological atmosphere was most probably composed of nitrogen, carbon dioxide, and water vapor, resulting from volatile outgassing, as opposed to the older view of a strongly reducing early atmosphere composed of methane, ammonia, and hydrogen. Photochemical calculations indicate that methane would have been readily destroyed via reaction with the hydroxyl radical produced from water vapor and that ammonia would have been readily lost via photolysis and rainout. The rapid loss of methane and ammonia, coupled with the absence of a significant source of these gases, suggest that atmospheric methane and ammonia were very short lived, if they were present at all. An early atmosphere of N2, CO2, and H2O is stable and leads to the chemical production of a number of atmospheric species of biological significance, including oxygen, ozone, carbon monoxide, formaldehyde, and hydrogen cyanide. Using a photochemical model of the early atmosphere, the chemical productionof these species over a wide range of atmospheric parameters were investigated. These calculations indicate that early atmospheric levels of O3 were significantly below the levels needed to provide UV shielding. The fate of volcanically emitted sulfur species, e.g., sulfur dioxide and hydrogen sulfide, was investigated in the early atmosphere to assess their UV shielding properties. The photochemical calculations show that these species were of insufficient levels, due in part to their short photochemical lifetimes, to provide UV shielding.

Levine, J. S.↗
NASA NTRS1986

Diagnostic analysis of two-dimensional monthly average ozone balance with Chapman chemistry

Chapman chemistry has been used in a two-dimensional model to simulate ozone balance phenomenology. The similarity between regions of ozone production and loss calculated using Chapman chemistry and those computed using LIMS and SAMS data with a photochemical equilibrium model indicate that such simplified chemistry is useful in studying gross features in stratospheric ozone balance. Net ozone production or loss rates are brought about by departures from the photochemical equilibrium (PCE) condition. If transport drives ozone above its PCE condition, then photochemical loss dominates production. If transport drives ozone below its PCE condition, then photochemical production dominates loss. Gross features of ozone loss/production (L/P) inferred for the real atmosphere from data are also simulated using only eddy diffusion. This indicates that one must be careful in assigning a transport scheme for a two-dimensional model that mimics only behavior of the observed ozone L/P.

Stolarski, Richard S.↗
NASA NTRS1992

Polycyclic aromatic hydrocarbons - Primitive pigment systems in the prebiotic environment

The chemical evolution of meteoritic organics in the primitive earth is examined experimentally with attention given to the photochemical effects of hydrocarbon/water mixtures. Also addressed are the generation of amphiphilic products by photochemical reactions and the transduction of light energy into potentially useful forms. Polycyclic aromatic hydrocarbons (PAHs) absorb light and exist in carbonaceous chondrites; PAHs are therefore examined as primitive pigments by means of salt solutions with pyrene, fluoranthene, and pyrene derivatives with hexadecane. The hexadecane undergoes photochemical oxidation and yields long-chain amphiphiles with oxygen supplied by water, and acid pH shifts also occur. PAHs are also tested in lipid bilayer membranes to examine light-energy transduction. Protons are found to accumulate within the membrane-bounded volume to form proton gradients, and this reaction is theorized to be a good model of primitive photochemical reactions that related to the transduction of light energy into useable forms.

Deamer, D. W.↗
NASA NTRS1992

Summertime photochemistry of the troposphere at high northern latitudes

Budgets of O3, NO(x), and NO(y), and acetic acid in the Arctic Boundary Layer Expedition (ABLE 3A) flight region are constructed using photochemical model statistics based on aircraft observations. A Lagrangian model is used to reconstruct the photochemical history of two aged biomass fire plumes sampled by the ABLE 3A aircraft. It is shown that anthropogenic influence on O3 levels in the Arctic may manifest itself not by long-range transport of pollution-derived O3, but rather by a decrease of the regional photochemical sink due to the presence of small amounts of NO(x). The low concentrations of NO(x) measured in ABLE 3A were sufficient to reduce the rate of photochemical loss appreciably relative to a NO(x)-free atmosphere, thus increasing the O3 lifetime. It is shown that decomposition of PAN can account for most of the NO(x) measured below 4-km altitude, but for only 20 percent at 6-km altitude. A lifetime of 29 days is estimated for NO(y) in the ABLE 23A flight region.

Jacob, D. J.↗
NASA NTRS1993

A photostationary state analysis of the NO2-NO system based on airborne observations from the subtropical/tropical North and South Atlantic

The Chemical Instrumentation Test and Evaluation 3 (CITE 3) NO-NO2 database has provided a unique opportunity to examine important aspects of tropospheric photochemistry as related to the rapid cycling between NO and NO2. Our results suggest that when quantitative testing of this photochemical system is based on airborne field data, extra precautions may need to be taken in the analysis. This was particularly true in the CITE 3 data analysis where different regional environments produced quite different results when evaluating the photochemical test ratio (NO2)(sub expt)/(NO2)(sub calc), designated here as R(sub E)/R(sub C). The quantity (NO2)(sub Calc) was evaluated using the following photostationary state expression: (NO2)(sub Calc) = k(sub 1)(O3) + k(sub 4)(HO2) + k(sub 5)(CH3O2) + k(sub 6)(RO2))(NO)(sub Expt)/J(sub 2). The four most prominent regional environmental data sets identified in this analysis were those labeled here as free-tropospheric northern hemisphere (FTNH), free-tropospheric tropical northern hemisphere (FTTNH), free-tropospheric southern hemisphere (FTSH), and tropical-marine boundary layer (plume) (TMBL(P)). The respective R(sub E)/R(sub C) mean and median values for these four data subsets were 1.74, 1.69; 3.00, 2.79; 1.01, 0.97; and 0.99, 0.94. Of the four data subsets listed, the two that were statistically the most robust were FTNH and FTSH; for these the respective R(sub E)/R(sub C) mean and standard deviation of the mean values were 1.74 +/- 0.07 and 1.01 +/- 0.04. The FTSH observations were in good agreement with theory, whereas those from the FTNH data set were in significant disagreement. An examination of the critical photochemical parameters O3, UV(zenith), NO, NO2, and non-methane hydrocarbons (NMHCs) for these two databases indicated that the most likely source of the R(sub E)/R(sub C) bias in the FTNH results was the presence of a systematic error in the observational data rather than a shortening in our understanding of fundamental photochemical processes. Although neither a chemical nor meteorological analyses of these data identified this error with complete certainty, they did point to the three most likely possibilities: (1) an NO2 interference from a yet unidentified NO(y) species: (2) the presence of unmeasured hydrocarbons, the integrated reactivity of which would be equivalent to approximately 2.7 parts per billion by volume (ppbv) of toluene; or (3) some combination of points (1) and (2). Details concerning hypotheses (1) and (2) as well as possible ways to minimize these problems in future airborne missions are discussed.

Davis, D. D.↗
NASA NTRS1994

Ocular hazards of light

The eye is protected against bright light by the natural aversion response to viewing bright light sources. The aversion response normally protects the eye against injury from viewing bright light sources such as the sun, arc lamps and welding arcs, since this aversion limits the duration of exposure to a fraction of a second (about 0.25 s). The principal retinal hazard resulting from viewing bright light sources is photoretinitis, e.g., solar retinitis with an accompanying scotoma which results from staring at the sun. Solar retinitis was once referred to as 'eclipse blindness' and associated 'retinal burn'. Only in recent years has it become clear that photoretinitis results from a photochemical injury mechanism following exposure of the retina to shorter wavelengths in the visible spectrum, i.e., violet and blue light. Prior to conclusive animal experiments at that time, it was thought to be a thermal injury mechanism. However, it has been shown conclusively that an intense exposure to short-wavelength light (hereafter referred to as 'blue light') can cause retinal injury. The product of the dose-rate and the exposure duration always must result in the same exposure dose (in joules-per-square centimeter at the retina) to produce a threshold injury. Blue-light retinal injury (photoretinitis) can result from viewing either an extremely bright light for a short time, or a less bright light for longer exposure periods. This characteristic of photochemical injury mechanisms is termed reciprocity and helps to distinguish these effects from thermal burns, where heat conduction requires a very intense exposure within seconds to cause a retinal coagulation otherwise, surrounding tissue conducts the heat away from the retinal image. Injury thresholds for acute injury in experimental animals for both corneal and retinal effects have been corroborated for the human eye from accident data. Occupational safety limits for exposure to UVR and bright light are based upon this knowledge. As with any photochemical injury mechanism must consider the action spectrum, which describes the relative effectiveness of different wavelengths in causing a photobiological effect. The action spectrum for photochemical retinal injury peaks at approximately 440 nm.

Sliney, David H.↗
NASA NTRS2004

Meridional Variations of C2H2 and C2H6 in Jupiter's Atmosphere from Cassini CIRS Infrared Spectra

Hydrocarbons such as acetylene (C2H2) and ethane (C2H6) are important tracers in Jupiter's atmosphere, constraining our models of the chemical and dynamical processes. However, our knowledge of the vertical and meridional variations of their abundances has remained sparse. During the flyby of the Cassini spacecraft in December 2000, the Composite Infrared Spectrometer (CIRS) instrument was used to map the spatial variation of emissions from 10-1400 cm(sup -1) (1000-7 microns). In this paper we analyze a zonally-averaged set of CIRS spectra taken at the highest (0.5 cm(sup -1)) resolution, to infer atmospheric temperatures in the stratosphere at 0.5-20 mbar via the v4 band of CH4, and in the troposphere at 150-400 mbar, via the H2 absorption at 600-800 cm(sup -1). Simultaneously, we retrieve the abundances of C2H2 and C2H6 via the v5 and vg bands respectively. Tropospheric absorption and stratospheric emission are highly anti-correlated at the CIRS resolution, introducing a non-uniqueness into the retrievals, such that vertical gradient and column abundance cannot both be found without additional constraints. Assuming profile gradients from photochemical calculations, we show that the column abundance of C2H2 decreases sharply towards the poles by a factor approximately 4, while C2H6 is unchanged in the north and increasing in the south, by a factor approximately 1.8. An explanation for the meridional trends is proposed in terms of a combination of photochemistry and dynamics. Poleward, the decreasing UV flux is predicted to decrease the abundances of C2H2 and C2H6 by factors 2.7 and 3.5 respectively at a latitude 70 deg. However, the lifetime of C2H6 in the stratosphere (5 x 10(exp 9)) is much longer than the dynamical timescale for meridional motions inferred from SL-9 debris (5 x 10(exp 8 s)), and therefore the constant or rising abundance towards high latitudes likely indicates that meridional mixing dominates over photochemical effects. For C2H2, the opposite occurs, with the relatively short photochemical lifetime (3 x 10(exp 7 s)), compared to meridional mixing times, ensuring that the expected photochemical trends are visible.

Nixon, C. A.↗
NASA NTRS2007

An Overview of Snow Photochemistry: Evidence, Mechanisms and Impacts

It has been shown that sunlit snow and ice plays an important role in processing atmospheric species. Photochemical production of a variety of chemicals has recently been reported to occur in snow/ice and the release of these photochemically generated species may significantly impact the chemistry of the overlying atmosphere. Nitrogen oxide and oxidant precursor fluxes have been measured in a number of snow covered environments, where in some cases the emissions significantly impact the overlying boundary layer. For example, photochemical ozone production (such as that occurring in polluted mid-latitudes) of 3-4 ppbv/day has been observed at South Pole, due to high OH and NO levels present in a relatively small boundary layer. Field and laboratory experiments have determined that the origin of the observed NOx flux is the photochemistry of nitrate within the snowpack, however some details of the mechanism have not yet been elucidated. A variety of low molecular weight organic compounds have been shown to be emitted from sunlit snowpacks, the source of which has been proposed to be either direct or indirect photo-oxidation of natural organic materials present in the snow. Although myriad studies have observed active processing of species within irradiated snowpacks, the fundamental chemistry occurring remains poorly understood. Here we consider the nature of snow at a fundamental, physical level; photochemical processes within snow and the caveats needed for comparison to atmospheric photochemistry; our current understanding of nitrogen, oxidant, halogen and organic photochemistry within snow; the current limitations faced by the field and implications for the future.

Grannas, A. M.↗