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At least 145 records · Page 8

Photodissociation of cyanoacetylene: Application to the atmospheric chemistry of Titan

The quantum yield and reaction threshold for the photochemical dissociation of cyanoacetylene into a hydrogen atom and the cyanoethynyl radical have been determined. The quantum yield at 185 nm is approximately 0.09. The threshold is approximately 240 nm. Combination of this data with literature values shows that production of excited-state cyanoacetylene is the major primary process resulting from irradiation between 185 and 254 nm. Also determined are the relative rate constants for the abstraction of a hydrogen atom from hydrogen, methane, and ethane by the cyanoethynyl radical (k(H2):k(CH4):k(C2H6) = 1:9.3:63). Implications of these results for the proposal that hydrogen abstraction plays an important role in the conversion of methane to ethane and in the protection of unsaturated compounds from photoconsumption in the atmosphere of Titan are discussed.

Clarke, David W.↗

Development of a two-stream mixing layer from tripped and untripped boundary layers

The effects of the state of the initial boundary layers on the development of a two-stream, plane mixing layer, with a velocity ratio of 0.6 are experimentally investigated. Spanwise-average profiles are compared for the first time. The results indicate that both the near and far-field growth rates for the untripped case are significantly higher than the tripped case. The maximum Reynolds stresses and higher-order products for the two cases behave very differently in the near-field, but asymptote to approximately the same constant levels far downstream. The mean velocity and turbulence profiles in this region also collapse adequately for the two cases when plotted in similarity coordinates. The distance required to achieve self-similarity is distinctly shorter for the tripped case, in contrast to previous observations. The higher growth rate for the untripped case is attributed to the presence of streamwise vortices which result in additional entrainment by the mixing layer.

Bell, James H.↗

The effects of arcjet operating condition and constrictor geometry on the plasma plume

Measurements of plasma number density and electron temperature were obtained in the plumes of lab arcjet thrusters using electrostatic probes of both spherical and cylindrical geometry. The two arcjet thrusters used had different constrictor and/or nozzle geometries and operated on mixtures of nitrogen, hydrogen, and ammonia to simulate the decomposition products of hydrazine and ammonia. An increase in the measured electron density was observed for both geometries with increasing arc power at a constant mass flow rate and with increasing mass flow rate at a constant arc current. For a given operating condition, the electron number density decreased exponentially off centerline and followed an inverse distance squared relationship along the thrust axis. Typical measured electron temperatures ranged from 0.1 to 0.2 eV.

Carney, Lynnette M.↗

The effects of arcjet thruster operating condition constrictor geometry on the plasma plume

Measurements of plasma number density and electron temperature were obtained in the plumes of lab arcjet thrusters using electrostatic probes of both spherical and cylindrical geometry. The two arcjet thrusters used had different constrictor and/or nozzle geometries and operated on mixtures of nitrogen, hydrogen, and ammonia to simulate the decomposition products of hydrazine and ammonia. An increase in the measured electron density was observed for both geometries with increasing arc power at a constant mass flow rate and with increasing mass flow rate at a constant arc current. For a given operating condition, the electron number density decreased exponentially off centerline and followed an inverse distance squared relationship along the thrust axis. Typical measured electron temperatures ranged from 0.1 to 0.2 eV.

Carney, Lynnette M.↗

The photophysics of monomeric bacteriochlorophylls c and d and their derivatives: properties of the triplet state and singlet oxygen photogeneration and quenching

Measurements of pigment triplet-triplet absorption, pigment phosphorescence and photosensitized singlet oxygen luminescence were carried out on solutions containing monomeric bacteriochlorophylls (Bchl) c and d, isolated from green photosynthetic bacteria, and their magnesium-free and farnesyl-free analogs. The energies of the pigment triplet states fell in the range 1.29-1.34 eV. The triplet lifetimes in aerobic solutions were 200-250 ns; they increased to 280 +/- 70 microseconds after nitrogen purging in liquid solutions and to 0.7-2.1 ms in a solid matrix at ambient or liquid nitrogen temperatures. Rate constants for quenching of the pigment triplet state by oxygen were (2.0-2.5) x 10(9) M-1 s-1, which is close to 1/9 of the rate constant for diffusion-controlled reactions. This quenching was accompanied by singlet oxygen formation. The quantum yields for the triplet state formation and singlet oxygen production were 55-75% in air-saturated solutions. Singlet oxygen quenching by ground-state pigment molecules was observed. Quenching was the most efficient for magnesium-containing pigments, kq = (0.31-1.2) x 10(9) M-1 s-1. It is caused mainly by a physical process of singlet oxygen (1O2) deactivation. Thus, Bchl c and d and their derivatives, as well as chlorophyll and Bchl a, combine a high efficiency of singlet oxygen production with the ability to protect photochemical and photobiological systems against damage by singlet oxygen.

NASA Discipline Number 52-30↗

Photochemistry of bromoacetylene - Formation of HBr and quenching of excited Br/4 2P 0 1/2/

The photolysis of bromacetylene is examined by means of vacuum ultraviolet flash photolysis-kinetic spectroscopy, with attention given to the production of Br atoms in the 2P 0 3/2 and 2P 0 1/2 states, the production of HBr, and UV absorption attributable to the ethynyl radical. Although Br(2P 0 1/2) and Br(2P 0 3/2) were both directly observed at the shortest delay time after the flash, strongly indicating the presence of the ethynyl radical, transient absorption by C2H was not detected in the range 125 to 180 nm. Quenching rate constants for the decay of the 2P 0 1/2 state of Br, which is observed to form concurrently with the ground state, are derived for quenching by He, CH2Br, CF4, and D2 from the pseudo-first-order decay rates. HBr was observed as a secondary photolysis product, and a model of its formation by the exothermic reaction of ground-state atoms with C2HBR, coupled with the secondary production of Br atoms, is found to agree well with the experiment.

Laufer, A. H.↗

Analysis of in Vitro Evolution Reveals the Underlying Distribution of Catalytic Activity Among Random Sequences

The emergence of catalytic RNA is believed to have been a key event during the origin of life. Understanding how catalytic activity is distributed across random sequences is fundamental to estimating the probability that catalytic sequences would emerge. Here, we analyze the in vitro evolution of triphosphorylating ribozymes and translate their fitnesses into absolute estimates of catalytic activity for hundreds of ribozyme families. The analysis efficiently identified highly active ribozymes and estimated catalytic activity with good accuracy. The evolutionary dynamics follow Fisher’s Fundamental Theorem of Natural Selection and a corollary, permitting retrospective inference of the distribution of fitness and activity in the random sequence pool for the first time. The frequency distribution of rate constants appears to be log-normal, with a surprisingly steep dropoff at higher activity, consistent with a mechanism for the emergence of activity as the product of many independent contributions.

Abe Pressman↗

Transport phenomena of reactive fluid flow in heterogeneous combustion processes.

A previously developed computer program was used to model two transient hybrid combustion processes involving tubes of solid Plexiglas. In the first study, representing combustion of a hybrid rocket, the oxidizing gas was oxygen, and calculations were continued sufficiently long to obtain steady-state values. Systematic variations were made in reaction rate constant, mass flow rate, and pressure, alternatively using constant and temperature dependent regression rate models for the fuel surface. Consistent results were obtained, as is evidenced by the values for the mass function of the reaction product and the flame temperature, for which plots are supplied. In the second study, fire initiation in a duct was studied, with an air mixture as the oxidizing gas. It was demonstrated that a satisfactory flame spread mechanism could be reproduced on the computer. In both of the above applications, the general, transient, two-dimensional conservation equations were represented, together with chemical reactions, solid-fuel interface conditions, and heat conduction in the solid fuel.

Hung, W. S. Y.↗

Role of the methylene amidogen (H2CN) radical in the atmospheres of Titan and Jupiter

The methylene amidogen (H2CN) radical can be shown to be an important intermediate in models for the formation of HCN (via N + CH3) and the recombination of H to H2 (via H + HCN) on Titan as well as in models for the formation of HCN (via NH2 + C2H3) in the atmosphere of Jupiter. Experiments in our laboratory in a discharge flow system with mass spectrometric detection of both reactants and products have established that the major product channel (90 percent for the reaction N + CH3 is that leading to H2CN + H. The same result was obtained for N + CD3 yields D2CN + D. The rate constant for the reaction D + D2CN yields DCN + D2 was measured for the first time and k(298 K) greater than 7 x 10(exp -11) cu cm/s was found. The same result was obtained for the H atom reaction. This is the final step in the reaction sequence leading to HCN on both Titan and Jupiter and to formation of H2 from H on Titan. The first measurement of the ionization potentials for H2CN and D2CN was also made. From electron impact studies I.P. = (9.6 + or - 1.0) eV was obtained for both radicals. An upperlimit of I.P. less than 11.6 eV came from observations of the H2CN radical by photoionization mass spectrometry using an Ar resonance lamp (106.7 nm). Further photoionization experiments are planned using synchrotron radiation plus monochromator as a tunable vacuum UV light source.

Nesbitt, F. L.↗

Possible role of NO3 in the nighttime chemistry of a cloud

The NO3 radical in the aqueous phase is a strong oxidizing agent which reacts rapidly with a wide variety of inorganic and organic species. Within nighttime clouds the production of gaseous NO3 from the reaction of NO2 with O3 followed by heterogeneous scavenging of NO3 by cloud droplets can represent a significant source of these reactive radicals to cloud water. Model calculations indicate that in addition to leading to the production of NO3(-) in cloud water, this aqueous-phase source of NO3 can, under the appropriate conditions and depending upon the values for a number of uncertain rate constants, have a significant impact upon the rate of conversion of SO2 to H2SO4.

Chameides, W. L.↗

Spatial distribution of H2O(+) in Comet P/Halley

Comet Halley spectroscopic and imaging data near the time of the Vega 1 encounter in March 1986 have been analyzed for H2O(+) distribution and near-nucleus ion physics, using a data-reduction procedure encompassing flat fielding, sky removal, continuum subtraction, contamination correction, absolute flux calibration, and conversion to ion-column densities. A 25,000 km-radius collision zone within which collisions dominate the solar wind's sweeping effect is verified. A production rate of H2O(+) ions is calculated on the basis of the average velocity and column density integral across the tail. An analysis of the tailward ion flow indicates constant acceleration beyond 130,000 km from the nucleus.

Disanti, Michael A.↗

Results of critical velocity experiments with barium, strontium, and calcium releases from CRRES satellite

As part of the NASA Combined Release and Radiation Effects Satellite (CRRES) chemical release program in September 1990, two Ba and also one each Sr and Ca canisters of a boron-titanium thermite mixture, which vaporizes the element on ignition, were released near perigee after dusk in the South Pacific to study the critical velocity effect proposed by Alfven. The critical velocities of these three elements are 2.7, 3.5, and 5.4 km/s respectively, all well below the orbital velocity of 9.4 km/s. On September 10, 1990, a Sr and Ba pair (G-13, or critical ionization velocity (CIV) I) was released near Rarotonga at approximately 515 km altitude in a background electron density of 3.4 x 10(exp 6)/cu cm. On September 14, 1990, G-14 or CIV II released a Ca and Ba pair west of New Caledonia near 595 km at an electron density of 1.5 x 10(exp 6)/cu cm. Ions of all three elements were observed with low-light level imagers from two aircraft after they had transited up the magnetic field lines into the sunlight. Emissions from the spherically expanding neutral gas shells below the solar terminator, observed with cameras filtered for the Ba(+) ion line at 4554 A and also in unfiltered imagers for approximately 15 s after release, are probably due to excitation by hot electrons created in the CIV process. The ions created clearly lost much of their energy, which we now show can be explained by elastic collisions: Ba(+) + O. Inventories of the observed ions indicate yields of 0.15% and 1.84% for Ba in the first and second experiments, 0.02% for Sr and 0.27% for Ca. Ionization from all the releases continued along the satellite trajectory much longer (greater than 45 s) than expected for a CIV process. The ion production along the satellite track versus time typically shows a rapid rise to a peak in a few seconds followed by an exponential decrease to a level essentially constant rate. The characteristic distances for CIV I and II are 47 and 62 km, respectively. We interpret the early time rise and exponential fall to be due to CIV ionization, of 0.014% (CIV I) and 0.40% (CIV II) for the Ba releases. The later ions produced at a constant rate probably have origins from other such processes as stripping and associative ionization collisions with atmospheric constituents primarily O, and charge exchange with O(+), He(+), and H(+). We suggest that the much larger Ba ionization rate in CIV II than CIV I is due to the fact that the release occurred in the peak Ca density where hot electrons were already present.

Wescott, E. M.↗

Flash spectroscopic studies of the kinetics of the halorhodopsin photocycle

The photoreactions of halorhodopsin are complicated by the fact that the parent pigment and its photoproducts interact with chloride. Thus, in any photoreaction scheme at least four species have to be accounted for: HR565 and HR578 Cl-, as well as HR640 and HR520 Cl-. A photocycle scheme proposed earlier places the two main photointermediates of halorhodopsin, HR520 Cl- and HR640, into a single photocycle, with a chloride-dependent equilibrium between them [Oesterhelt, D., Hegemann, P., & Tittor, J. (1985) EMBO J. 4, 2351-2356]. This scheme, with the additional feature of direct photoproduction of HR640 from HR565, was tested in this work by using numerical solutions of the appropriate differential equations to simulate flash-induced absorption changes at 500 nm (production of HR520 Cl-) and at 660 nm (production of HR640). The time scale of the simulation was ms following the flash. Comparison of the simulated curves with experimental traces yielded a unique set of three rate constants. The proposed photocycle scheme and these rate constants predict well the shapes and amplitudes of flash traces at various chloride concentrations. It appears from the photocycle scheme, and the numerical values of rate constants, that chloride is bound with high affinity to the parent halorhodopsin molecule, but with much lower affinity to its main photointermediate. This may be the consequence of the fact that in the parent halorhodopsin in the retinal configuration is all-trans, but in the two photointermediates it is 13-cis.

Non-NASA Center↗

Gas core reactors for actinide transmutation

The preliminary design of a uranium hexafluoride actinide transmutation reactor to convert long-lived actinide wastes to shorter-lived fission product wastes was analyzed. It is shown that externally moderated gas core reactors are ideal radiators. They provide an abundant supply of thermal neutrons and are insensitive to composition changes in the blanket. For the present reactor, an initial load of 6 metric tons of actinides is loaded. This is equivalent to the quantity produced by 300 LWR-years of operation. At the beginning, the core produces 2000 MWt while the blanket generates only 239 MWt. After four years of irradiation, the actinide mass is reduced to 3.9 metric tonnes. During this time, the blanket is becoming more fissile and its power rapidly approaches 1600 MWt. At the end of four years, continuous refueling of actinides is carried out and the actinide mass is held constant. Equilibrium is essentially achieved at the end of eight years. At equilibrium, the core is producing 1400 MWt and the blanket 1600 MWt. At this power level, the actinide destruction rate is equal to the production rate from 32 LWRs.

Clement, J. D.↗

Changes in the High-latitude Ocean as Possible Causes of Atmospheric CO2 Variations

Measurements on air enclosed in old polar ice have indicated that the atmospheric CO2 concentration was ca. 50 to 70 ppm lower in late glacial times than during the Holocene. Similar measurements performed on samples from a Greenland ice core, dating ca. 30,000 to 40,000 B.P., and have yielded evidence of several CO2 oscillations with an amplitude of ca. 50 ppm. Each change lasted on the order of a few centuries. A mechanism by which circulation changes in the high-latitude ocean could lead to rapid variations in atmospheric CO2 is proposed. In the Antarctic Ocean a slowing down of the vertical mixing would imply a smaller upward flux of sigma CO2 and nutrients. Assuming constant productivity, sigma CO2 and nutrients would be more completely used which would imply lower CO2 in these high-latitude surface waters. In areas with a warm surface, a slowing down of the circulation would not have a direct impact on CO2 because productivity would automatically decrease by the same factor as the upwelling rate of nutrients. Studies with a simple box model of the ocean-atmosphere system suggest that a suddent decrease by a factor of 2 of the water exchange between the surface and deep sea in high latitudes could lead to a CO2 decrease of ca. 40 to 50 ppm with a time constant of ca. 200 years. Deep-sea sediment studies indicate rapid changes in the high-latitude surface conditions of the North Atlantic and the Antarctic Oceans at the end of the last glaciation. Studies of carbon isotope ratios should help ascertain whether this proposed mechanism was indeed responsible for the CO2 variation.

Siegenthaler, U.↗

The Northeast Monsoon's Impact on Mixing, Phytoplankton Biomass and Nutrient Cycling in the Arabian Sea

In the northern Arabian Sea, atmospheric conditions during the Northeast (winter) Monsoon lead to deep convective mixing. Due to the proximity of the permanent pyncnocline to the sea surface, this mixing does not penetrate below 125 m. However, a strong nitracline is also present and the deep convection results in significant nitrate flux into the surface waters. This leads to nitrate concentrations over the upper 100 m that exceed 4 micrometers toward the end of the Monsoon. During the 1994/1995 US JGOFS/Arabian Sea expedition, the mean areal gross primary production over two successive Northeast Monsoons was determined to be 1.35gC/sq m/d. Thus, despite the deep penetrative convection, high rates of primary productivity were maintained. An interdisciplinary model was developed to elucidate the biogeochemical processes involved in supporting the elevated productivity. This model consists of a 1-D mixed-layer model coupled to a set of equations that tracked phytoplankton growth and the concentration of the two major nutrients (nitrate and ammonium). Zooplankton grazing was parameterized by rate constant determined by shipboard experiments. Model boundary conditions consist of meteorological time-series measured from the surface buoy that was part of the ONR Arabian Sea Experiment's central mooring. Our numerical experiments show that elevated surface evaporation, and the associated salinization of the mixed layer, strongly contributes to the frequency and penetration depth of the observed convective mixing. Cooler surface temperatures, increased nitrate entrainment, reduced water column stratification, and lower near-surface chlorophyll a concentrations all result from this enhanced mixing. The model also captured a dependence on regenerated nitrogen observed in nutrient uptake experiments performed during the Northeast Monsoon. Our numerical experiments also indicate that variability in mean pycnocline depth causes up to a 25% reduction in areal chlorophyll a concentration. We hypothesize that such shifts in pycnocline depth may contribute to the interannual variations in primary production and surface chlorophyll a concentration that have been previously observed in this region.

Wiggert, J. D.↗

Electrochemical Technology for Oxygen Removal and Measurement in the CELSS Test Facility, Engineering Development Unit

The Life Support Flight Program is evaluating regenerative technologies, including those that utilize higher plants, as a means to reduce resupply over long duration space missions. Constructed to assist in the evaluation process is the CELSS Test Facility Engineering Development Unit (CTF-EDU) an environmentally closed (less than 1% mass and thermal leakage) technology test bed. This ground based fully functional prototype is currently configured to support crop growth, utilizing the power, volume and mass resources allocated for two space station racks. Sub-system technologies were selected considering their impact on available resources, their ability to minimize integration issues, and their degree of modularity. Gas specific mass handling is a key sub-system technology for both biological and physical/chemical life support technologies. The CTF-EDU requires such a system to accommodate non-linear oxygen production from crops, by enabling the control system to change and sustain partial pressure set points in the growth volume. Electrochemical cells are one of the technologies that were examined for oxygen handling in the CTF-EDU. They have been additionally considered to meet other regenerative life support functions, such as oxygen generation, the production of potable water from composite waste streams, and for having the potential to integrate life support functions with those of propulsion and energy storage. An oxygen removal system based on an electrochemical cell was chosen for the EDU due to it's low power, volume and mass requirements (10W, 0.000027 cu m, 4.5 kg) and because of the minimal number of integration considerations. Unlike it's competitors, the system doesn't require post treatments of its byproducts, or heat and power intensive regenerations, that also mandate system redundancy or cycling. The EDUs oxygen removal system only requires two resources, which are already essential to controlled plant growth: electricity and water. Additionally, the amount of oxygen that is removed from the EDU is directly proportional to the cell input current via Faraday's constant, potentially allowing for a mol/electron measurement of photosynthetic rate. The currently operative oxygen removal system has maintained reduced oxygen set points within the EDU, and preparation is underway to verify of the accuracy of electrochemical measurement of oxygen production and hence, photosynthesis. This paper examines the working principles of the electrochemical cell, outlines the overall design of the oxygen removal system and its integration with other EDU subsystems, and summarizes test results obtained over crop growth cycles in the CTF-EDU.

Drews, Michael E.↗

Adaptation to delayed auditory feedback

Delayed auditory feedback disrupts the production of speech, causing an increase in speech duration as well as many articulatory errors. To determine whether prolonged exposure to delayed auditory feedback (DAF) leads to adaptive compensations in speech production, 10 subjects were exposed in separate experimental sessions to both incremental and constant-delay exposure conditions. Significant adaptation occurred for syntactically structured stimuli in the form of increased speaking rates. After DAF was removed, aftereffects were apparent for all stimulus types in terms of increased speech rates. A carry-over effect from the first to the second experimental session was evident as long as 29 days after the first session. The use of strategies to overcome DAF and the differences between adaptation to DAF and adaptation to visual rearrangement are discussed.

Katz, D. I.↗