Initiation reactions in the high temperature decomposition of styrene.

The thermal decomposition of styrene was investigated in a combined experimental, theory and modeling study with particular emphasis placed on the initial dissociation reactions. Two sets of shock tube/time-of-flight mass spectrometry (TOF-MS) experiments were performed to identify reaction products and their order of appearance. One set of experiments was conducted with a miniature high repetition rate shock tube at the Advanced Light Source at Lawrence Berkeley National Laboratory using synchrotron vacuum ultraviolet photoionization. The other set of experiments was performed in a diaphragmless shock tube (DFST) using electron impact ionization. The datasets span 1660-2260 K and 0.5-12 atm. The results show a marked transition from aromatic products at low temperatures to polyacetylenes, up to C8H2, at high temperatures. The TOF-MS experiments were complemented by DFST/LS (laser schlieren densitometry) experiments covering 1800-2250 K and 60-240 Torr. These were particularly sensitive to the initial dissociation reactions. These reactions were investigated theoretically and revealed the dissociation of styrene to be a complex multichannel process with strong pressure and temperature dependencies that were evaluated with multi-well master equation simulations. Simulations of the LS data with a mechanism developed in this work are in excellent agreement with the experimental data. From these simulations, rate coefficients for the dissociation of styrene were obtained that are in good agreement with the theoretical predictions. The simulation results also provide fair predictions of the temperature and pressure dependencies of the products observed in the TOF-MS studies. Prior experimental studies of styrene pyrolysis concluded that the main products were benzene and acetylene. In contrast, this study finds that the majority of styrene dissociates to create five styryl radical isomers. Of these, α-styryl accounts for about 50% with the other isomers consuming approximately 20%. It was also found that C-C bond scission to phenyl and vinyl radicals consumes up to 25% of styrene. Finally the dissociation of styrene to benzene and vinylidene accounts for roughly 5% of styrene consumption. Comments are made on the apparent differences between the results of this work and prior literature.

Effects of climate change on residential infiltration and air pollution exposure.

Air exchange through infiltration is driven partly by indoor/outdoor temperature differences, and as climate change increases ambient temperatures, such differences could vary considerably even with small ambient temperature increments, altering patterns of exposures to both indoor and outdoor pollutants. We calculated changes in air fluxes through infiltration for prototypical detached homes in nine metropolitan areas in the United States (Atlanta, Boston, Chicago, Houston, Los Angeles, Minneapolis, New York, Phoenix, and Seattle) from 1970-2000 to 2040-2070. The Lawrence Berkeley National Laboratory model of infiltration was used in combination with climate data from eight regionally downscaled climate models from the North American Regional Climate Change Assessment Program. Averaged over all study locations, seasons, and climate models, air exchange through infiltration would decrease by ~5%. Localized increased infiltration is expected during the summer months, up to 20-30%. Seasonal and daily variability in infiltration are also expected to increase, particularly during the summer months. Diminished infiltration in future climate scenarios may be expected to increase exposure to indoor sources of air pollution, unless these ventilation reductions are otherwise compensated. Exposure to ambient air pollution, conversely, could be mitigated by lower infiltration, although peak exposure increases during summer months should be considered, as well as other mechanisms.

Flame experiments at the advanced light source: new insights into soot formation processes.

The following experimental protocols and the accompanying video are concerned with the flame experiments that are performed at the Chemical Dynamics Beamline of the Advanced Light Source (ALS) of the Lawrence Berkeley National Laboratory(1-4). This video demonstrates how the complex chemical structures of laboratory-based model flames are analyzed using flame-sampling mass spectrometry with tunable synchrotron-generated vacuum-ultraviolet (VUV) radiation. This experimental approach combines isomer-resolving capabilities with high sensitivity and a large dynamic range(5,6). The first part of the video describes experiments involving burner-stabilized, reduced-pressure (20-80 mbar) laminar premixed flames. A small hydrocarbon fuel was used for the selected flame to demonstrate the general experimental approach. It is shown how species' profiles are acquired as a function of distance from the burner surface and how the tunability of the VUV photon energy is used advantageously to identify many combustion intermediates based on their ionization energies. For example, this technique has been used to study gas-phase aspects of the soot-formation processes, and the video shows how the resonance-stabilized radicals, such as C3H3, C3H5, and i-C4H5, are identified as important intermediates(7). The work has been focused on soot formation processes, and, from the chemical point of view, this process is very intriguing because chemical structures containing millions of carbon atoms are assembled from a fuel molecule possessing only a few carbon atoms in just milliseconds. The second part of the video highlights a new experiment, in which an opposed-flow diffusion flame and synchrotron-based aerosol mass spectrometry are used to study the chemical composition of the combustion-generated soot particles(4). The experimental results indicate that the widely accepted H-abstraction-C2H2-addition (HACA) mechanism is not the sole molecular growth process responsible for the formation of the observed large polycyclic aromatic hydrocarbons (PAHs).

Ramping up the Spallation Neutron Source beam power with the H- source using 0 mg Cs/day.

This paper describes the ramp up of the beam power for the Spallation Neutron Source by ramping up the pulse length, the repetition rate, and the beam current emerging from the H(-) source. Starting out with low repetition rates (< or = 10 Hz) and short pulse lengths (< or = 0.2 ms), the H(-) source and low-energy beam transport delivered from Lawrence Berkeley National Laboratory exceeded the requirements with almost perfect availability. This paper discusses the modifications that were required to exceed 0.2 ms pulse length and 0.2% duty factor with acceptable availability and performance. Currently, the source is supporting neutron production at 1 MW with 38 mA linac beam current at 60 Hz and 0.9 ms pulse length. The pulse length will be increased to approximately 1.1 ms to meet the requirements for neutron production with a power between 1 and 1.4 MW. A medium-energy beam transport (MEBT) beam current of 46 mA with a 5.4% duty factor has been demonstrated for 32 h. A 56 mA MEBT beam current with a 4.1% duty factor has been demonstrated for 20 min at the conclusion of a 12-day production run. This is close to the 59 mA needed for 3 MW neutron productions. Also notable is the Cs(2)CrO(4) cesium system, which dispenses approximately 10 mg of Cs during the startup of the ion source, sufficient for producing the required 38 mA for 4 weeks without significant degradation.

Lightest isotope of Bh produced via the 209Bi(52Cr,n)260Bh reaction.

The lightest isotope of Bh was produced in the new 209Bi(52Cr,n)260Bh reaction at the Lawrence Berkeley National Laboratory's 88-Inch Cyclotron. Positive identification was made by observation of eight correlated alpha particle decay chains in the focal plane detector of the Berkeley Gas-Filled Separator. 260Bh decays with a 35(-9)(+19) ms half-life by alpha particle emission mainly by a group at 10.16 MeV. The measured cross section of 59(-20)(+29) pb is compared to model predictions. The influence of the N=152 and Z=108 shells on alpha decay properties is discussed.

Direct detection of polyynes formation from the reaction of ethynyl radical (C2H) with propyne (CH3-C[triple bond]CH) and allene (CH2=C=CH2).

The reactions of the ethynyl radical (C(2)H) with propyne and allene are studied at room temperature using an apparatus that combines the tunability of the vacuum ultraviolet radiation of the Advanced Light Source at Lawrence Berkeley National Laboratory with time-resolved mass spectrometry. The C(2)H radical is prepared by 193-nm photolysis of CF(3)CCH and the mass spectrum of the reacting mixture is monitored in time using synchrotron-photoionization with a dual-sector mass spectrometer. Analysis using photoionization efficiency curves allows the isomer-specific detection of individual polyynes of chemical formula C(5)H(4) produced by both reactions. The product branching ratios are estimated for each isomer. The reaction of propyne with ethynyl gives 50-70% diacetylene (H-C[triple bond]C-C[triple bond]C-H) and 50-30% C(5)H(4), with a C(5)H(4)-isomer distribution of 15-20% ethynylallene (CH(2)=C=CH-C[triple bond]CH) and 85-80% methyldiacetylene (CH(3)-C[triple bond]C-C[triple bond]CH). The reaction of allene with ethynyl gives 35-45% ethynylallene, 20-25% methyldiacetylene and 45-30% 1,4-pentadiyne (HC[triple bond]C-CH(2)-C[triple bond]CH). Diacetylene is most likely not produced by this reaction; an upper limit of 30% on the branching fraction to diacetylene can be derived from the present experiment. The mechanisms of polyynes formation by these reactions as well as the implications for Titan's atmospheric chemistry are discussed.

BNCT dose distribution in liver with epithermal D-D and D-T fusion-based neutron beams.

Recently, a new application of boron neutron capture therapy (BNCT) treatment has been introduced. Results have indicated that liver tumors can be treated by BNCT after removal of the liver from the body. At Lawrence Berkeley National Laboratory, compact neutron generators based on (2)H(d,n)(3)He (D-D) or (3)H(t,n)(4)He (D-T) fusion reactions are being developed. Preliminary simulations of the applicability of 2.45 MeV D-D fusion and 14.1 MeV D-T fusion neutrons for in vivo liver tumor BNCT, without removing the liver from the body, have been carried out. MCNP simulations were performed in order to find a moderator configuration for creating a neutron beam of optimal neutron energy and to create a source model for dose calculations with the simulation environment for radiotherapy applications (SERA) treatment planning program. SERA dose calculations were performed in a patient model based on CT scans of the body. The BNCT dose distribution in liver and surrounding healthy organs was calculated with rectangular beam aperture sizes of 20 cm x 20 cm and 25 cm x 25 cm. Collimator thicknesses of 10 and 15 cm were used. The beam strength to obtain a practical treatment time was studied. In this paper, the beam shaping assemblies for D-D and D-T neutron generators and dose calculation results are presented.

Visualizing rhizosphere chemistry of legumes with mid-infrared synchrotron radiation.

A bright synchrotron light source operated by the Lawrence Berkeley National Laboratory served as an external source for infrared (IR) microscopy of plant root microcosms. Mid-IR light from synchrotrons is 2-3 orders of magnitude brighter than conventional sources, providing contrast based on the chemical information in the reflected signal at a spatial resolution near the diffraction-limit of 3-10 microm. In an experiment using plant root microcosms fitted with zinc selenide IR-transmissive windows (50 mm x 20 mm x 1 mm), we describe chemical differences and similarities within the root zone of mung bean (Vigna radiata L.), grown with or without phosphorus, and revealed by reflectance spectromicroscopy. Comparative root and root-exudate profiles are described in sand/silt culture over the wavelength range of 2.5 to 16 pm (4.000 to 650 cm(-1) ) in the mid-IR. the spectral region most useful for the analytical identification of small organic molecules. Root epidermal tissue of plants grown with low phosphorus showed a greater lipid contribution and less lignin than nutrient-sufficient plants. In the zone 200 microm from the root axis, control plants were enriched with simple sugars and monomeric lignin precursors. In low-phosphorus plants, the rhizosphere possessed IR signatures from protein and sugars. Individual soil minerals could be easily discriminated from biological material. Synchrotron IR spectromicroscopy, therefore, complements existing root imaging techniques.

Advances in the automated detection of metaphase chromosomes labeled with fluorescence dyes.

Applications of fluorescence in situ hybridization (FISH) for translocation studies and biological dosimetry would benefit substantially from reliable and efficient automatic detection of metaphase chromosomes labeled with fluorescent dyes. We replicated and evaluated a fluorescence metaphase finder previously developed at the Medical Research Council (MRC), Human Genetics Unit (Scotland) and at Lawrence Berkeley Laboratory (LBL; California). The MRC/LBL system seemed to detect nearly all of the metaphases on the test slides, but it presented an unacceptable number of false positives (about five false positives per one true positive). Furthermore, we determined that the system actually overcalled true detections by counting certain metaphase spreads twice (duplicates). Through modifications of the MRC/LBL system, we developed the Lawrence Livermore National Laboratory (LLNL) system, which minimizes the detection of duplicates, incorporates new detection features, uses a binary decision tree (BDT) for classification, and provides functionalities to improve scanning accuracy and improve the post-detection review. To test the new system, DAPI-stained preparations of metaphase chromosomes from blood lymphocytes of four unrelated donors were placed on slides in drops ranging from 7 mm to 20 mm in diameter. Drops contained between 5 and 200 scorable metaphases each. The LLNL system achieved approximately 90% detection of non-duplicated metaphases as verified by an expert cytogeneticist, with typically less than one false positive per every one true positive detected.