SEARCH · Search NASA
Results for “photochemically”
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.
Photochemical and kinetic measurements of atmospheric constituents vis-a-vis their role in controlling stratospheric ozone
Explore the source record for details and available documents.
Photochemical reactions of various model protocell systems
Models for the emergence of cellular life on the primitive Earth, and for physical environments of that era have been studied that embody these assumptions: (1) pregenetic cellular forms were phase-bounded systems primarily photosynthetic in nature, and (2) the early Earth environment was anoxic (lacking appreciable amounts of free hydrogen). It was found that organic structures can also be formed under anoxic conditions (N2, CO3=, H2O) by protracted longwavelength UV radiation. Apparently these structures form initially as organic layers upon CaCO3 crystalloids. The question remains as to whether the UV photosynthetic ability of such phase bounded structures is a curiosity, or a general property of phase bounded systems which is of direct interest to the emergence of cellular life. The question of the requirement and sailient features of a phase boundary for UV photosynthetic abilities was addressed by searching for similar general physical properties which might be manifest in a variety of other simple protocell-like structures. Since it has been shown that laboratory protocell models can effect the UV photosynthesis of low molecular weight compounds, this reaction is being used as an assay to survey other types of structures for similar UV photosynthetic reactions. Various kinds of structures surveyed are: (1) proteinoids; (2) liposomes; (3) reconstituted cell membrane spheroids; (4) coacervates; and (5) model protocells formed under anoxic conditions.
A dynamically based transport parameterization for one-dimensional photochemical models of the stratosphere
The net vertical tracer flux in the stratosphere is due primarily to advection by the global-scale mean meridional circulation, not to diffusion by turbulent eddies. Using a simple model of this circulation, it is shown that the net flux can be approximated by a flux-gradient relationship in which the vertical 'eddy transport' coefficient is proportional to the square of the diabatic heating rate and inversely proportional to the rate at which meridional tracer gradients are destroyed by horizontal eddy mixing and chemical damping. Thus the transport coefficient will differ for tracers with differing chemical lifetimes. Profiles computed for various source gases (CH4 N2O, CF2Cl2, and CFCl3) show that this parameterization provides an improvement over conventional formulations that utilize a single transport coefficient for all species.
Photochemical consequences of enhanced CO2 levels in earth's early atmosphere
Greatly enhanced atmospheric CO2 concentrations are the most likely mechanism for offsetting the effects of reduced solar luminosity early in the earth's history. CO2 levels of 80 to 600 times the present value could have maintained a mean surface temperature of 0 C to 15 C, given a 25 percent decrease in solar output. Such high CO2 levels are at least qualitatively consistent with the present understanding of the carbonate-silicate geochemical cycle. The presence of large amounts of CO2 has important implications for the composition of the earth's prebiotic atmosphere. The hydrogen budget of a high-CO2 primitive atmosphere would have been strongly influenced by rainout of H2O2 and H2CO. The reaction of H2O2 with dissolved ferrous iron in the early oceans could have been a major sink for atmospheric oxygen. The requirement that this loss of oxygen be balanced by a corresponding loss of hydrogen (by escape to space and rainout of H2CO) implies that the atmospheric H2 mixing ratio was greater than 2 x 10 to the -5th and the ground level O2 mixing ratio was below 10 to the -12th, even if other surface sources of H2 were small. These results are only weakly dependent on changes in solar UV flux, rainout rates, and vertical mixing rates in the primitive atmosphere.
Photochemical production of H2SO4 aerosols on Venus
The quantum yields for producing O2(a (1 delta g)) and O2(b(1 sigma g +)) for the reaction, O + ClO yields Cl + O2, are summarized. Also included are results for other simple reactions capable of producing the singlet oxygen states. An episodic injection of SO2 into the upper atmosphere of Venus is considered as a possible explanation for the airglow values.
Electronic energy transfer and quenching in copolymers of styrene and 2-(2-prime-hydroxy -5-prime-vinylphenyl)-2H-benzotriazole Photochemical processes in polymeric systems. X
Intensity and lifetime quenching of the polystyrene monomer and excimer fluorescence emission by a pendant quencher have been studied in the solid state and in solution for a series of copolymers of styrene and 2-(2-prime-hydroxy-5-prime-vinylphenyl)-2H-benzotriazole. Two mechanisms of quenching have been identified. One involves interception of the migrating monomer excitation by the quencher, and the other involves a single-step Foerster energy-transfer process from the excimer traps to a quencher. The relative efficiencies of these two quenching mechanisms in the solid state and in solution have been compared and related to the efficiency of electronic energy migration. An estimate of the excimer trap concentration in solid polystyrene is also reported.
Photochemical and thermal modeling in the early atmosphere of the earth
The simplest carbon compounds, present in the terrestrial and planetary atmospheres, exhibit a wide range of oxidation states, carbon dioxide and methane being the most oxidized and the most reduced form of carbon, respectively. The question arises as to the origin and the interconversion among the carbon species. The chemical pathways for the conversion of CH4 to CO and CO2 are for the most part known. The reverse process, the reduction of CO to CH4 is however, poorly understood. A new reaction is proposed, H2CO + H + M yields CH3O + M, which might play a fundamental role in the reduction of CO or CH4. An update is presented of nitrile photochemistry on Titan.
Diagnostic studies of the HxOy-NzOy-O3 photochemical system using data from NASA GTE field expeditions
Spring 1084 GTE CITE-1 flight data from the field exercise was obtained from a GTE Data Archive Tape. Chemical and supporting meteorological data taken over the Pacific Ocean was statistically and diagnostically analyzed to identify the key processes affecting the concentrations of ozone and its chemical precursors in the region. The analysis was completed. The analysis of the GTE CITE-2 data is being performed in collaboration with Dr. D.D. Davis and other GTE scientists. Initial results of the analysis were presented and work begun on the paper describing the results.
Photochemical fractionation of O-16 in the space medium modeled by resonance excitation of CO by H-Lyman alpha
Analyses of meteorite matter, the present structure of the solar system, and the evolution of matter in stellar systems are used to provide inferences concerning the formation of primordial matter in the solar system. Results indicate that molecular excitation processes similar to those observed today in circumstellar regions and dark interstellar clouds were operating in the early solar nebula. It is suggested that resonance excitation of broad isotopic bands by strong UV line sources may have resulted in the anomalous isotopic compositions noted in meteorites.
Photochemical stability of CO2 in the Martian atmosphere - Reevaluation of the eddy diffusion coefficient and the role of water vapor
Theoretical models of CO2 photodissociation in the atmosphere of Mars are developed and analyzed, with a focus on the conditions prevailing during the Mariner 6/7 experiments. The aeronomy of Martian CO2 is reviewed; the atomic O distribution in the upper atmosphere is characterized; the construction of the basic model is described; and simulation results are presented in extensive tables and graphs and discussed in detail. The vertical eddy-diffusion coefficient corresponding to the estimated upper-atmosphere O density (1-2 percent at 135 km) is found to be about 5 x 10 to the 7th sq cm/sec, and HO(x) is found to play a significant role in catalyzing the recombination of CO and O to form CO2. The reasons why the model overpredicts the production of HO(x) and hence of CO2 are explored.
Spatial variations of the 3 micron emission features within UV-excited nebulae - Photochemical evolution of interstellar polycyclic aromatic hydrocarbons
Spectra at 3 microns have been obtained at several positions in the Orion Bar region and in the nebula surrounding HD 44179. Weak emission features at 3.40, 3.46, 3.51, and 3.57 microns are prominent in the Orion Bar region. The 3.40- and 3.51-micron features increase in intensity relative to the dominant 3.29-micron feature. The spectrum obtained in the Red Rectangle region 5 arcsecs north of HD 44179 are similar to those in the Orion Bar, with a weak, broad 3.40-micron feature at the position of HD 44179. The spatial behavior of the weak emission features is explained in terms of hot bands of the CH stretch and overtones, and combination bands of other fundamental vibrations in simple PAHs. Based on the susceptibility of PAHs to destruction by the far UV fields in both regions, PAH sizes are estimated at 20-50 carbon atoms.
Photochemical approaches to ordered polymers
The photocyclization of o-benzyloxyphenyl ketone chromophores provides an efficient, high yield route to the synthesis of 2,3-diphenylbenzofurans. The synthesis and solution of photochemistry of a series of polymers containing this chromophore is described. The photocuring of these polymers is a potential new approach to the synthesis of highly conjugated polymers based upon a p-phenylene bisbenzofuran repeat unit.
On the explicit versus family solution of the fully diurnal photochemical equations of the stratosphere
The family approach used to solve chemical equations is examined by integrating a heirarchy of versions of a 2D model of stratospheric chemistry and transport on an isentropic surface. Errors of up to 20 percent in radical concentrations can result from the use of a small number of families; the use of more families increases the accuracy of the solutions. The minimum number of families which can be used to provide an accurate solution is discussed, and the parameterization of long-time-scale species is recommended for making the model more efficient. The most pervasive errors are found in calculations of the concentrations of radical species, a problem which can lead to errors in predicting O3 over the long run. Methods for improving the schemes are presented, emphasizing the possibility of producing an improved 3D model.
Photochemical partitioning of the reactive nitrogen and chlorine reservoirs in the high-latitude stratosphere
The correlated set of measurements in the lower stratosphere from polar missions of the NASA ER-2 is used to derive partitioning of the major components of the reactive nitrogen and inorganic chlorine reservoirs. The results provide a consistent method for comparing distributions, and hence the controlling processes, between different areas of the near-polar regions. Clear evidence of the effects of heterogeneous processes in the atmosphere is found. Values for NO2, ClONO2, N2O5, and Cl2O2 are derived in a simplified steady-state model based on in situ NO, ClO, O3, temperature, and pressure measurements, laboratory-measured reaction rates; and modeled photodissociation rates. Values for the reservoir totals are independently derived from measurements of N2O, organic chlorine, and total reactive nitrogen. The relative abundances of the measured and derived species within the reservoirs are calculated, and the longer-lived species HCl and HNO3 are estimated as the residuals of their respective reservoirs.
Comet Halley as an aggregate of interstellar dust and further evidence for the photochemical formation of organics in the interstellar medium
Photolysis of mixtures of CO:NH3:H2O at 12 K results in the formation of an organic residue which is not volatile in high vacuum at room temperature. Analysis of this fraction by GC-MS resulted in the detection of C2-C3 hydroxy acids and hydroxy amides, glycerol, urea, glycine, hexamethylene tetramine, formamidine and ethanolamine. Use of isotopically labeled gases made it possible to establish that the observed products were not contaminants. The reaction pathways for the formation of these products were determined from the position of the isotopic labels in the mass spectral fragments. The significance of these findings to the composition of comets and the origins of life is discussed.
Modified HNO3 seasonality in volcanic layers of a polar ice core - Snow-pack effect or photochemical perturbation?
Changes in atmospheric HNO3 chemistry following the Laki (1783), Tambora (1815), and Katmai (1912) volcanic eruptions are presently investigated in view of a central Greenland ice core's chemical composition. Attention is given to the concentration of several cations and anions, using ion chromatography. Following the eruptions, the ratio of winter to summer depositions of NO3(-) was significantly higher than during nonvolcanic periods. While this may be due to ice pack effects, it is proposed that large concentrations of the stratospheric H2SO4 particles ejected by the volcanoes favored HNO3 removal during Arctic winter.
Diagnostic studies of the HxOy-NxOy-O3 photochemical system using data from NASA GTE field expeditions
The research effort supported in part by the subject grant focused on three related topics. Our major effort was concentrated on the analysis of data gathered during GTE field expeditions. Ancillary efforts were directed at: the development and application of a Global Chemical Transport Model for the study of the atmospheric reactive nitrogen budget; the development and application of a one-dimensional, time dependent cloud model for the study of the impact of in-cloud aqueous phase chemistry on the atmospheric sulfur budget; and mechanistic studies of the chemical processes involved in dry deposition of ozone to vegetative surfaces. In the sections below, we briefly summarize the central conclusions of each of these efforts. These discussions are followed by a listing of the papers completed during the granting period and the graduate students supported by funds from the grant. Reprints and preprints of all papers completed with support from the grant are attached as appendices.