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At least 505 records · Page 28

Synchrotron Photoionization Mass Spectrometry Measurements of Kinetics and Product Formation in the Allyl Radical (H2CCHCH2)Self Reaction

Product channels for the self-reaction of the resonance-stabilized allyl radical, C3H5 + C3H5, have been studied with isomeric specificity at temperatures from 300-600 K and pressures from 1-6 Torr using time-resolved multiplexed photoionization mass spectrometry. Under these conditions 1,5-hexadiene was the only C6H10 product isomer detected. The lack of isomerization of the C6H10 product is in marked contrast to the C6H6 product in the related C3H3 + C3H3 reaction, and is due to the more saturated electronic structure of the C6H10 system. The disproportionation product channel, yielding allene + propene, was also detected, with an upper limit on the branching fraction relative to recombination of 0.03. Analysis of the allyl radical decay at 298 K yielded a total rate coefficient of (2.7 +/- 0.8) x 10(exp -11) cu cm/molecule/s, in good agreement with pre.vious experimental measurements using ultraviolet kinetic absorption spectroscopy and a recent theoretical determination using variable reaction coordinate transition state theory. This result provides independent indirect support for the literature value of the allyl radical ultraviolet absorption cross-section near 223 nm.

Selby, Talitha M.↗

Satellite-Detected Ocean Ecosystem Response to Volcanic Eruption in the Subarctic Northeast Pacific Ocean

Volcanic eruptions in the Aleutian archipelago during the summer of 2008 deposited large quantities of iron-laden ash to the Subarctic North Pacific Ocean. The surface ocean ecosystem response has been previously characterized using limited in situ and autonomous field measurements and numerical modeling, but basin-scale satellite remote sensing has been limited to a simple description of chlorophyll variability. Here, we show that the ecosystem response is a complex combination of phytoplankton biomass and physiology that can be described with satellite ocean color diagnostics such as the chlorophyll to carbon biomass ratio (Chl:Cphyto) and chlorophyll fluorescence yield. Together, these quantities outline a more complete picture of ecological response spanning unique signals of iron stress (and relief from), photo acclimation, changes in phytoplankton growth rate, increases in biomass, and timescales of decay for these processes.

Ocean Ecosystem↗

Satellite‐Detected Ocean Ecosystem Response to Volcanic Eruptions in the Subarctic Northeast Pacific Ocean

Volcanic eruptions in the Aleutian Archipelago during the summer of 2008 deposited large quantities of iron‐laden ash to the subarctic North Pacific Ocean. The surface ocean ecosystem response has been previously characterized using limited in situ and autonomous field measurements and numerical modeling, but basin‐scale satellite remote sensing has been limited to a simple description of chlorophyll variability. Here, we show that the ecosystem response is a complex combination of phytoplankton biomass and physiology that can be described with satellite ocean color diagnostics such as the chlorophyll‐to‐carbon biomass ratio (Chl:Cphyto) and chlorophyll fluorescence yield. Together, these quantities outline a more complete picture of ecological responses spanning unique signals of iron stress (and relief from), photo acclimation, changes in phytoplankton growth rate, increases in biomass, and timescales of decay for these processes.

T.K. Westberry↗

H2/O2 three-body rates at high temperatures

Hydrogen atoms are produced in the presence of excess O2, and the first-order decay are studied as a function of temperature and pressure in order to obtain the rate coefficient for the three-body reaction between H-atoms and O2. Attention is focused on the kinetic scheme employed as well as the reaction cell and photolysis and probe laser system. A two-photon laser-induced fluorescence technique is employed to detect H-atoms without optical-thickness or O2-absorption problems. Results confirm measurements reported previously for the H + O2 + N2 reaction at 300 K and extend these measurements to higher temperatures. Preliminary data indicate non-Arrehenius-type behavior of this reaction rate coefficient as a function of temperature. Measurements of the rate coefficient for H + O2 + Ar reaction at 300 K give a rate coefficient of 2.1 +/- 0.1 x 10 to the -32nd cm exp 6/molecule sec.

Marinelli, William J.↗

Supergranule Diffusion and Active Region Decay

Models of the Sun's magnetic dynamo include turbulent diffusion to parameterize the effects of convective motions on the evolution of the Sun's magnetic field. Supergranules are known to dominate the evolution of the surface magnetic field structure as evidenced by the structure of both the active and quiet magnetic network. However, estimates for the dif hivity attributed to su perymules differ by an order of magnitude from about 100 km sup2/s to more than 1000 km sup2/s. We examine this question of the e i v i t y using three merent approaches. 1) We study the decay of more than 30,000 active regions by determining the rate of change in the sunspot area of each active region from day-to-day. 2) We study the decay of a single isolated active region near the time of solar minimum by examining the magnetic field evolution over five solar rotations fiom SOHOMDI magnetograms obtained at 96-minute intervals. 3) We study the characteristics of supergranules that influence the estimates of their diffusive properties - flow speeds and lifetimes as functions of size - fiom SOHO/MDI Dopplergrams.

Hathaway, David H.↗

The recombination epoch revisited

Previous studies of cosmological recombination have shown that this process produces as a by-product a highly superthermal population of Ly-alpha photons which retard completion of recombination. Cosmological redshifting was thought to determine the frequency distribution of the photons, while two-photon decay of hydrogen's 2s state was thought to control their numbers. It is shown here that frequency diffusion due to photon scattering dominate the cosmological redshift in the frequency range near line center which fixes the ratio of ground state to excited state population, while incoherent scattering into the far-red damping wing effectively destroys Ly-alpha photons as a rate which is competitive with two-photon decay. The former effect tends to hold back recombination, while the latter tends to accelerate it; the net results depends on cosmological parameters, particularly the combination Omega(b) h/sq rt (2q0), where Omega(b) is the fraction of the critical density provided by baryons.

Krolik, Julian H.↗

Rate constant for the reaction SO + BrO yields SO2 + Br

The rate of the radical-radical reaction SO + BrO yields SO2 + Br has been determined at 298 K in a discharge flow system near 1 torr pressure with detection of SO and BrO via collision-free sampling mass spectrometry. The rate constant was determined using two different methods: measuring the decay of SO radicals in the presence of an excess of BrO and measuring the decay of BrO radicals in excess SO. The results from the two methods are in reasonable agreement and the simple mean of the two values gives the recommended rate constant at 298 K, k = (5.7 + or - 2.0) x 10 to the -11th cu cm/s. This represents the first determination of this rate constant and it is consistent with a previously derived lower limit based on SO2 formation. Comparison is made with other radical-radical reactions involving SO or BrO. The reaction SO + BrO yields SO2 + Br is of interest for models of the upper atmosphere of the earth and provides a potential coupling between atmospheric sulfur and bromine chemistry.

Brunning, J.↗

Scale Dependence of Statistics of Spatially Averaged Rain Rate Seen in TOGA COARE Comparison with Predictions from a Stochastic Model

A characteristic feature of rainfall statistics is that they in general depend on the space and time scales over which rain data are averaged. As a part of an earlier effort to determine the sampling error of satellite rain averages, a space-time model of rainfall statistics was developed to describe the statistics of gridded rain observed in GATE. The model allows one to compute the second moment statistics of space- and time-averaged rain rate which can be fitted to satellite or rain gauge data to determine the four model parameters appearing in the precipitation spectrum - an overall strength parameter, a characteristic length separating the long and short wavelength regimes and a characteristic relaxation time for decay of the autocorrelation of the instantaneous local rain rate and a certain 'fractal' power law exponent. For area-averaged instantaneous rain rate, this exponent governs the power law dependence of these statistics on the averaging length scale $L$ predicted by the model in the limit of small $L$. In particular, the variance of rain rate averaged over an $L \times L$ area exhibits a power law singularity as $L \rightarrow 0$. In the present work the model is used to investigate how the statistics of area-averaged rain rate over the tropical Western Pacific measured with ship borne radar during TOGA COARE (Tropical Ocean Global Atmosphere Coupled Ocean Atmospheric Response Experiment) and gridded on a 2 km grid depends on the size of the spatial averaging scale. Good agreement is found between the data and predictions from the model over a wide range of averaging length scales.

Kundu, Prasun K.↗

Absolute rate parameters for the reaction of atomic hydrogen with hydrazine

Absolute rate parameters for the reaction of atomic hydrogen with hydrazine H + N2H4 yields H2 + N2H3 have been determined in a direct manner using flash photolysis of dilute mixtures of hydrazine in helium and time dependent observation of H via resonance fluorescence. By measuring the H-atom decay under pseudo-first-order conditions, the bimolecular rate constant K sub 1 was obtained over the temperature range 228-400 K. The data were fitted with good linearity to the Arrhenius expression K sub 1 = (9.87 plus or minus 1.17) x 10 to the -12th exp(-2380 plus or minus 100/RT) cu cm/molecule/s. The data were shown to be free of any contributions from secondary reactions involving H as a reactant or product.

Stief, L. J.↗

Background events in microchannel plates

Measurements have been made to assess the characteristics and origins of background events in microchannel plates (MCPs). An overall background rate of about 0.4 events/sq cm persec has been achieved consistently for MCPs that have been baked and scrubbed. The temperature and gain of the MCPs are found to have no significant effect on the background rate. Detection of 1.46-MeV gamma rays from the MCP glass confirms the presence of K-40, with a concentration of 0.0007 percent, in MCP glass. It is shown that beta decay from K-40 is sufficient to cause the background rate and spectrum observed. Anticoincidence measurements indicate the the background rate caused by cosmic ray interactions is small (less than 0.016 events/sq cm per sec).

Siegmund, O. H. W.↗

Radiation from plutonium 238 used in space applications

The principal mode of the nuclear decay of plutonium 238 is by alpha particle emission at a rate of 17 curies per gram. Gamma radiation also present in nuclear fuels arises primarily from the nuclear de-excitation of daughter nuclei as a result of the alpha decay of plutonium 238 and reactor-produced impurities. Plutonium 238 has a spontaneous fission half life of 4.8 x 10 to the 10th power years. Neutrons associated with this spontaneous fission are emitted at a rate of 28,000 neutrons per second per gram. Since the space fuel form of plutonium 238 is the oxide pressed into a cermet with molybdenum, a contribution to the neutron emission rate arises from (alpha, n) reactions with 0-17 and 0-18 which occur in natural oxygen.

Keenan, T. K.↗

A molecular beam mass spectrometric study of the formation and photolysis of C(lc)lO dimer

A study of the chlorine oxides present at temperatures and pressures typical of the Antarctic stratosphere was carried out. A series of low temperature flow reactors was constructed and used in conjunction with molecular beam mass spectrometric techniques to identify species and characterize their kinetic behavior at temperatures of -20 to -70 C and pressures of from 30 to 130 Torr. It was found that the gas phase chlorine-oxygen system was quite complex at low temperatures. ClO dimer was identified and found to be thermodynamically very stable under stratospheric conditions. It was also found that any system which contained ClO also contained a larger oxide. The oxide was identified as Cl2O3. A survey of possible higher oxides, which have been postulated as possible chlorine sinks in the stratosphere, was also carried out. The rate of formation of ClO dimer was measured as a function of temperature and pressure. Measurements were made of both the decay of ClO and the formation of the dimer. By comparing these rates it was determined that virtually all of the ClO was converted to the dimer under stratospheric conditions, and that the other ClO reactions were not important under these conditions.

Greene, Frank T.↗

Rate constant for formation of chlorine nitrate by the reaction ClO + NO2 + M

The pseudo-first-order decay of ClO in a large excess of NO2 was monitored in a discharge flow/mass-spectrometer apparatus in order to measure the rate constant of the reaction ClO + NO2 + M yields ClONO2 + M for M = He, Ar, and N2 over the temperature range from 248 to 417 K. Numerical results are given for He at 248, 299, 360, and 417 K (1 to 9 torr); for Ar at 298 K (1 to 4 torr); and for N2 at 299, 360, and 417 K (1 to 6 torr). Systematic errors are estimated, and identification of the reaction product is discussed. The results obtained are shown to be in excellent agreement with other recent measurements of the same rate constant.

Leu, M. T.↗

Stability of the equilibrium for atomic H in solid H2

The previously reported phenomenological rate process theory for the storage of atomic hydrogen free radicals in a tritium-impregnated crystalline molecular hydrogen solid is used to determine the dynamical stability of the constant uniform equilibrium solution. The analysis indicates that the equilibrium is unstable (thus, unattainable experimentally) for storage temperatures in a certain range (specifically between 0.134 and 0.80 K for 0.03% tritium by weight, and between 0.165 and 0.80 K for 1.20% tritium by weight), while being absolutely stable with respect to arbitrary small-amplitude perturbations for all storage temperatures below and above this range. The theory also predicts the maximum size for a stable H/H2 sample with an appreciable concentration of trapped H and a net excess rate of volumetric heating due to the tritium decay.

Rosen, G.↗

Primary cosmic ray positrons and galactic annihilation radiation

The observation (Leventhal et al, 1978) of positron annihilation radiation at 0.511 MeV from the direction of the Galactic Center is reexamined, suggesting the possibility of a primary positron component of the cosmic rays. The observed 0.511 MeV emission requires a positron production rate nearly two orders of magnitude greater than the production rate of secondary cosmic ray positrons from pion decay produced in cosmic ray interactions. Possible sources of positrons are reviewed with both supernovae and pulsars appearing to be the more likely candidates. If only about 1% of these positrons were accelerated along with the cosmic ray nucleons and electrons to energies not less than 100 MeV, it is believed that these primary positrons would be comparable in intensity to those secondary positrons resulting from pion decay. Some observational evidence for the existence of primary positrons in the cosmic rays is also discussed.

Lingenfelter, R. E.↗

Formation processes and time scales for meteorite parent bodies

The transition from small particles suspended in the solar nebula to the planetesimals (asteroids) that became the parent bodies of meteorites is examined. Planetesimals probably grew by coagulation of grain aggregates that collided due to different rates of settling and drag-induced orbital decay. Their growth was accompanied by radial transport of solids, possibly sufficient to deplete the primordial mass in the asteroid zone, but with relatively little mixing. The formation of asteroid-sized planetesimals was probably rapid, on a time scale less than 1 Myr.

Weidenschilling, S. J.↗

Mode-medium instability and its correction with a Gaussian reflectivity mirror

A high power CO2 laser beam is known to deteriorate after a few microseconds due to a mode-medium instability (MMI) which results from an intensity dependent heating rate related to the vibrational-to-translational decay of the upper and lower CO2 lasing levels. An iterative numerical technique is developed to model the time evolution of the beam as it is affected by the MMI. The technique is used to study the MMI in an unstable CO2 resonator with a hard-edge output mirror for different parameters like the Fresnel number and the gas density. The results show that the mode of the hard edge unstable resonator deteriorates because of the diffraction ripples in the mode. A Gaussian-reflectivity mirror was used to correct the MMI. This mirror produces a smoother intensity profile which significantly reduces the effects of the MMI. Quantitative results on peak density variation and beam quality are presented.

Webster, K. L.↗