Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Radiolysis”

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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
NASA NTRS2011

Radiolysis of Sulfuric Acid, Sulfuric Acid Monohydrate, and Sulfuric Acid Tetrahydrate and Its Relevance to Europa

We report laboratory studies on the 0.8 MeV proton irradiation of ices composed of sulfuric acid (H2SO4), sulfuric acid monohydrate (H2SO4 H2O), and sulfuric acid tetrahydrate (H2SO4 4H2O) between 10 and 180 K. Using infrared spectroscopy, we identify the main radiation products as H2O, SO2, (S2O3)x, H3O+, HSO4(exp -), and SO4(exp 2-). At high radiation doses, we find that H2SO4 molecules are destroyed completely and that H2SO4 H2O is formed on subsequent warming. This hydrate is significantly more stable to radiolytic destruction than pure H2SO4, falling to an equilibrium relative abundance of 50% of its original value on prolonged irradiation. Unlike either pure H2SO4 or H2SO4 H2O, the loss of H2SO4 4H2O exhibits a strong temperature dependence, as the tetrahydrate is essentially unchanged at the highest irradiation temperatures and completely destroyed at the lowest ones, which we speculate is due to a combination of radiolytic destruction and amorphization. Furthermore, at the lower temperatures it is clear that irradiation causes the tetrahydrate spectrum to transition to one that closely resembles the monohydrate spectrum. Extrapolating our results to Europa s surface, we speculate that the variations in SO2 concentrations observed in the chaotic terrains are a result of radiation processing of lower hydration states of sulfuric acid and that the monohydrate will remain stable on the surface over geological times, while the tetrahydrate will remain stable in the warmer regions but be destroyed in the colder regions, unless it can be reformed by other processes, such as thermal reactions induced by diurnal cycling.

Loeffler, M. J.↗
NASA NTRS2022

Rapid Radiolytic Degradation of Amino Acids in the Martian Shallow Subsurface: Implications for the Search for Extinct Life

Amino acids are fundamental to life as we know them as the monomers of proteins and enzymes. They are also readily synthesized under a variety of plausible prebiotic conditions and are common in carbon-rich meteorites. Thus, they represent a reasonable class of organics to target in the search for prebiotic chemistry or chemical evidence of life on Mars. However, regardless of their origin, amino acids and other organic molecules present in near-surface regolith and rocks on Mars can be degraded by exposure to cosmic rays that can penetrate to a depth of a few meters. We exposed several pure amino acids in dry and hydrated silicate mixtures and in mixtures of silicates with perchlorate salts to gamma radiation at various temperatures and radiation doses representative of the martian near-subsurface. We found that irradiation of amino acids mixed with dry silica powder increased the rate of amino acid radiolysis, with the radiolysis constants of amino acids in silicate mixtures at least a factor of 10 larger compared with the radiolysis constants of amino acids alone. The addition of perchlorate salts to the silicate samples or hydration of silicate samples further accelerated the rate of amino acid destruction during irradiation and increased the radiolysis constants by a factor of *1.5. Our results suggest that even low-molecular-weight amino acids could degrade in just *20 million years in the top 10 cm of the martian surface regolith and rock, and even faster if the material contains elevated abundances of hydrated silicate minerals or perchlorates. We did not detect evidence of amino acid racemization after gamma radiation exposure of the samples, which indicates that the chirality of some surviving amino acids may still be preserved. Our experimental results suggest serious challenges for the search of ancient amino acids and other potential organic biosignatures in the top 2 m of the martian surface.

Alexander A. Pavlov↗
NASA NTRS1979

The radioracemization of isovaline - Cosmochemical implications

The optically pure D- and L-enantiomers of isovaline, which cannot be racemized by ordinary chemical mechanisms involving alpha-hydrogen removal and which has been isolated in apparently racemic form from the Murchison meteorite, have been subjected to partial radiolysis by the ionizing radiation from a 3000-Ci Co-60 gamma-ray source. Both in the anhydrous and hydrated solid states and as solid sodium or hydrochloride salts each enantiomer suffered significant radioracemization of the undestroyed residue during its partial radiolysis. The sodium salt of isovaline in 0.1-M aqueous solution suffered extensive radiolysis with relatively small radiation doses, but showed no detectable radioracemization. The significance of these observations with respect to the primordial enantiomeric composition of the isovaline (and other amino acids) indigenous to meteorites is discussed.

Bonner, W. A.↗
NASA NTRS1984

Beta-decay, Bremsstrahlen, and the origin of molecular chirality

A brief review is presented of the Vester-Ulbricht beta-decay Bremsstrahlen hypothesis for the origin of optical activity, and of subsequent experiments designed to test it. Certain experiments along these lines, begun in 1974 and involving the irradiation of racemic and optically active amino acids in a 61.7 KCi Sr-90-Y-90 Bremsstrahlen source, have now been completed and are described. After 10.89 years of irradiation with a total Bremsstrahlen dose of 2.5 x 10 to the 9th rads, crystalline DL-leucine, norleucine, and norvaline suffered 47.2, 33.6, and 27.4 percent radiolysis, respectively, but showed no evidence whatsoever of asymmetric degradation. Dand L-Leucine underwent about 48 percent radiolysis and showed 2.4-2.9 percent radioracemization. Other samples in solution were too severely degraded to analyze. Probable intrinsic reasons for the failure of the Vester-Ulbricht mechanism to afford asymmetric radiolysis in the present and related experiments involving beta-decay Bremsstrahlen are enumerated.

Bonner, W. A.↗
NASA NTRS1985

New estimates of asymmetric decomposition of racemic mixtures by natural beta-radiation sources

Some recent calculations that appeared to invalidate the Vester-Ulbricht hypothesis, which suggests that the chirality of biological molecules originates from the beta-radiolysis of prebiotic racemic mixtures, are reexamined. These calculations apparently showed that the radiolysis-induced chiral polarization can never exceed the chiral polarization produced by statistical fluctuations. It is here shown that several overly restrictive conditions were imposed on these calculations which, when relaxed, allow the radiolysis-induced polarization to exceed that produced by statistical fluctuations, in accordance with the Vester-Ulbricht hypothesis.

Hegstrom, R. A.↗
NASA NTRS1973

Radiolytic preparation of anhydrous tin (2) chloride

Anhydrous tin (2) chloride (SnCl2) is prepared by radiolysis with high energy electrons of a tin (4) chloride (SnCl4) solution in heptane. The SnCl4 is reduced to insoluble SNCl2. The energy yield, G(SnCl2), molecules of SnCl2, produced per 100 eV, increases with SnCl4 concentration from 1.6 at 0.15 M SnCl4 to 3.1 at 3.0 M SnCl4. Other parameters such as temperature total dose and beam current have little influence on G(SnCl2). The method may be used to prepare other metal halides if the higher valence, more covalent metal halide is soluble in aliphatic hydrocarbons and the lower more ionic metal halide is insoluble. The reaction mechanism is discussed; the radiolysis of both heptane and SnCl4 is involved. At high SnCl4 concentration G(SnCl2) appears to be limited by the yield of SnC13 radicals.

Philipp, W. H.↗
NASA NTRS1984

Experimental evidence for beta-decay as a source of chirality by enantiomer analysis

Earlier experiments testing the Vester-Ulbricht beta-decay hypothesis for the origin of molecular chirality are reviewed, followed by descriptions of experiments involving attempted asymmetric radiolysis of DL-amino acids using quantitative gas chromotography as a probe for optical activity. The radiation sources included Sr-90-Y-90, C-14, and P-32 Bremsstrahlen, longitudinally polarized electrons from a linear accelerator and longitudinally polarized protons from a cyclotron. With the possible exception of the linear accelerator irradiations, these experiments failed to produce g.c.-detectable enantiomeric excesses, even at 50-70 percent gross radiolysis. Thus no unambiguous support for the Vester-Ulbricht hypothesis is found in any of the attempted asymmetric radiolyses performed to date. Radioracemization, a possible reason for these failures, is discussed.

Bonner, W. A.↗
NASA NTRS1986

Origin of life and iron-rich clays

The premise that life began with self-replicating iron-rich clays is explored. In association with these clays and UV light, polar organic molecules, such as oxalic acid, were synthesized. The carbonaceous chondrites have both iron-rich clays and organic molecules. It is convenient to classify meteoritic organic matter into 3 categories: insoluble polymer, hydrocarbons and polar organics (soluble in water). Recent work on the delta D, delta N-15 and delta C-13 has made it clear that these three fractions have been made by three different mechanisms. A significant fraction of the insoluble polymer has a delta-D which suggests that it was made in an interstellar medium. The hydrocarbons seem to have been made on a parent body by a Fischer-Tropsch mechanism. The polar organics were probably synthesized in a mixture of carbonate (NH4)2CO3, Fe(++) ion and liquid water by radiolysis. In a set of experiments the radiolysis of (NH4)2CO3 in the presence and absence of Fe(++) ion has been examined. The synthesis of glycine in the presence of Fe(++) ion is 3-4 times that in the absence of ferrous ion. The effects of the addition of hydrocarbons to this mixture are explored. Iron-rich clays at low temperature and pressure are synthesized. So far the results are not sufficiently crystalline to look for replication. It should be noted that organic chelating agents such as oxalic acid do increase the crystallinity of the clays but not sufficiently. The hydrothermal synthesis of iron-rich clays is being examined.

Hartman, H. H.↗
NASA NTRS1987

Chemical processes in Triton's atmosphere and surface

The Neptune moon Triton may have an appreciable atmosphere; the preliminary calculations of Delitsky (1983) have suggested that there should be a significant resultant chemistry in a possible N2 ocean with dissolved CH4, given charged-particle radiolysis of gaseous mixtures and gamma radiolysis of N2-CH4 solutions. The latter will yield substantial quantities of organic products which will be partially soluble in any N2-CH4 liquid present. Attention is presently given to the energy sources available for Triton, in order to estimate rates of synthesis and ascertain the possible history of such simple and complex organic products on Triton's surface.

Delitsky, M. L.↗
NASA NTRS2001

Physical State of Ices in the Outer Solar System

Comparison of the identity and abundances of ices observed around protostars and those associated with comets clearly suggests that comets preserve the heritage of the interstellar materials that aggregated to form them. However, the ability to identify these same species on icy satellites in the outer solar system is a complex function of the composition of the original ices, their subsequent thermal histories, and their exposure to various radiation environments. Our ability to identify the ices currently present on objects in the outer solar system relies upon observational and laboratory, and theoretical efforts. To date there is ample observational evidence for crystalline water ice throughout the outer solar system. In addition, there is growing evidence that amorphous ice may be present on some bodies. More volatile ices, e.g. N2, CH4. CO, and other species, e.g. ammonia hydrate, are identified on objects lying at and beyond Uranus. Both photolysis and radiolysis play important roles in altering the original surfaces due to chemical reactions and erosion of the surface. Ultraviolet photolysis appears to dominate alteration of the upper few hundred Angstroms, although sputtering the surface can sometimes be a significantly competitative process; dominating on icy surfaces embedded in a strong planetary magnetospheric field. There is growing observational evidence that the by-products of photolysis and radiolysis, suggested on a theoretical basis, are present on icy surfaces.

Roush, Ted L.↗
NASA NTRS2002

The Diverse Surface Compositions of the Galilean Satellites

The galilean satellites represent a diverse collection, ranging from the volcanic moon Io, with a surface that is changing yearly, to Callisto, with a dark, ancient surface overlying ice. The composition of these surfaces are also quite different due to a variety of processes and influences, including tidal heating, radiolysis, gardening, a magnetic field (Ganymede), and meteoritic infall. Io's surface contains large quantities of sulfur dioxide (SO2) and colorful sulfur allotropes, both originating in plumes and flows from the tidally driven volcanoes. A broad, 1-micron band is found at high latitudes and may be due to absorption by long-chain sulfur polymers produced by SO2 radiolysis, although iron and iron sulfide compounds are candidates. An unidentified 3.15 micron absorber is equatorially distributed while a 4.62 micron band, perhaps due to a sulfate compound, exhibits a non-uniform distribution. Hot spots are generally dark, and some exhibit negative reflectance slopes (i.e., blue). The composition of these lavas has not been established spectroscopically, but the high temperatures of some volcanoes suggest ultramafic silicates or perhaps more refractory material such as oxides.

Carlson, R. W.↗
NASA NTRS2012

New Modeling Approaches to Study DNA Damage by the Direct and Indirect Effects of Ionizing Radiation

DNA is damaged both by the direct and indirect effects of radiation. In the direct effect, the DNA itself is ionized, whereas the indirect effect involves the radiolysis of the water molecules surrounding the DNA and the subsequent reaction of the DNA with radical products. While this problem has been studied for many years, many unknowns still exist. To study this problem, we have developed the computer code RITRACKS [1], which simulates the radiation track structure for heavy ions and electrons, calculating all energy deposition events and the coordinates of all species produced by the water radiolysis. In this work, we plan to simulate DNA damage by using the crystal structure of a nucleosome and calculations performed by RITRACKS. The energy deposition events are used to calculate the dose deposited in nanovolumes [2] and therefore can be used to simulate the direct effect of the radiation. Using the positions of the radiolytic species with a radiation chemistry code [3] it will be possible to simulate DNA damage by indirect effect. The simulation results can be compared with results from previous calculations such as the frequencies of simple and complex strand breaks [4] and with newer experimental data using surrogate markers of DNA double ]strand breaks such as . ]H2AX foci [5].

Plante, Ianik↗
NASA NTRS2016

The Spectrum of Jupiter's Great Red Spot: The Case for Ammonium Hydrosulfide (NH4SH)

Here we present new ultraviolet-visible spectra of irradiated ammonium hydrosulfide (NH4SH), a reported Jovian atmospheric cloud component, for a range of temperatures and radiation doses and make assignments to the spectral features. We show that the combination of radiolysis and thermal annealing of NH4SH causes the originally featureless ultraviolet-visible reflectance spectrum to evolve into one that absorbs in the ultraviolet-visible region. Furthermore, we find that our laboratory spectra resemble HST (Hubble Space Telescope) spectra below 500 nanometers, suggesting that the more stable reaction products of NH4SH radiolysis are likely an important component of the Great Red Spot.

Jupiter's Great Red Spot (GRS)↗