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At least 19 records

A Variable, Ultra-Short Pathlength Solution Cell for XAFS Transmission Spectroscopy of the Light Elements

We describe an x-ray absorption spectroscopy (XAS) cell that is suitable for solution-phase studies of the light elements in the series from Na+ and Ca2+. This ultra-short pathlength cell has a pathlength that can be remotely adjusted using a miniature stepper-motor drive and thereby readily provides transmission pathlengths in the range from submicron to several hundred microns. The flexibility to vary the pathlength enables acquisition of high-quality XAS spectra and also allows one to check for potential distortions in the spectra from thickness effects. The primary components are mostly commercially available optical parts. The performance of this device is demonstrated at the Cl K-edge (2.8 keV) for several different aqueous Cl- solutions. This work was supported by the US Department of Energy's (DOE) Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. PNNL is operated for the Department of Energy by Battelle.

low-Z cell↗

Temporally and spatially resolved X-ray densitometry in a shock tube

Gas densities were measured by x-ray absorption spectroscopy to examine spatial inhomogeneity in density behind incident and reflected shock waves in a miniature (12.7 mm bore) high repetition rate shock tube. Shock waves were generated in argon. The pressure and temperature behind the incident shock were P 2 ~ 1.72 bar and T 2 ~ 800 K, while those behind the reflected shock were P 5 ~ 6.5 bar and T 5 ~ 1480 K. Time-resolved line-of-sight transmission measurements using x-rays at 9 keV photon energy were made along various axial and transverse locations covering the entire shock tube cross section. The x-ray transmission at each location was converted to pathlength-integrated densities, which in some conditions could be further converted to pathlength-averaged densities. The measured gas densities were compared with those calculated by the normal shock wave relations, and good agreement was found in the preshock and immediately behind the incident shock regions. Similar agreement was found for reflected shock conditions very near the endwall. However, increasingly large differences between the measured and calculated gas densities were found as distance from the endwall increased. Furthermore, reconstruction by Abel inversion allowed time and radially resolved densities to be obtained from the transverse measurements. While the profiles measured in this experiment are of insufficient signal-to noise level and resolution to definitively assign boundary layer thicknesses, future improvements may be able to do this. The radially resolved densities reveal growing sidewall thermal boundary layers in gases behind the reflected shock. These reconstructions were compared with a model of the thermal boundary layer and are consistent with values of the thermal boundary layer thickness being between 0.25 mm and 1 mm at 0.7 ms after shock reflection.

42 ENGINEERING↗

Verification of Dose Distribution in Carbon Ion Radiation Therapy for Stage I Lung Cancer

Purpose: To evaluate robustness of dose distribution of carbon-ion radiation therapy (C-ion RT) in non-small cell lung cancer (NSCLC) and to identify factors affecting the dose distribution by simulated dose distribution. Methods and Materials: Eighty irradiation fields for delivery of C-ion RT were analyzed in 20 patients with stage I NSCLC. Computed tomography images were obtained twice before treatment initiation. Simulated dose distribution was reconstructed on computed tomography for confirmation under the same settings as actual treatment with respiratory gating and bony structure matching. Dose-volume histogram parameters, such as %D95 (percentage of D95 relative to the prescribed dose), were calculated. Patients with any field for which the %D95 of gross tumor volume (GTV) was below 90% were classified as unacceptable for treatment, and the optimal target margin for such cases was examined. Results: Five patients with a total of 8 fields (10% of total number of fields analyzed) were classified as unacceptable according to %D95 of GTV, although most patients showed no remarkable change in the dose-volume histogram parameters. Receiver operating characteristic curve analysis showed that tumor displacement and change in water-equivalent pathlength were significant predictive factors of unacceptable cases (P<.001 and P=.002, respectively). The main cause of degradation of the dose distribution was tumor displacement in 7 of the 8 unacceptable fields. A 6-mm planning target volume margin ensured a GTV %D95 of >90%, except in 1 extremely unacceptable field. Conclusions: According to this simulation analysis of C-ion RT for stage I NSCLC, a few fields were reported as unacceptable and required resetting of body position and reconfirmation. In addition, tumor displacement and change in water-equivalent pathlength (bone shift and/or chest wall thickness) were identified as factors influencing the robustness of dose distribution. Such uncertainties should be regarded in planning.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Development of an Attenuated Total Reflectance–Ultraviolet–Visible Probe for the Online Monitoring of Dark Solutions

Optical spectroscopy is a valuable tool for on-line monitoring of a variety of processes. Ultraviolet-visible (UV-vis) spectroscopy in particular, can monitor the concentration of analytes as well as identify speciation and oxidation state. However, it can be difficult to impossible to employ UV-vis based sensors on chemical systems that are very dark (i.e., high optical density) as exceedingly short pathlengths are required (for transmission approaches) or effective means of backscattering are needed (for reflectance approaches). Examples of processes that would benefit significantly from the use of optical sensors and encounter these challenges include used nuclear fuel recycling and molten salts with high concentrations of dissolved uranium. Utilizing an attenuated total reflectance (ATR) UV-vis approach can overcome these challenges and allow for the measurement of solutions orders of magnitude more concentrated than transmission UV-vis. However, determining ideal sensor specifications for varied processes can be time consuming and expensive. Here, in this study, we evaluate the ability for a novel ATR-UV-vis probe to measure very concentrated solutions of Co(II) and Ni(II) nitrate as well as organic dyes (methylene blue, acid red 1, and crystal violet). This sensor design provides a modular method for exploring possible “pathlengths” by altering the exposed ATR fiber length. Also studied were approaches to loading and measuring the sensor cell. These results are compared to a traditional 1 cm cuvette measured by transmission UV-vis. It was found that the ATR-UV-vis probe was capable of measuring solutions 600 times more concentrated than the 1 cm cuvette. Advanced data analysis in the form of multivariate curve resolution (MCR) was used to analyze the speciation of methylene blue over a large concentration range. The application of this novel ATR-UV-vis probe to the interrogation of dark solutions is a promising avenue for use in on-line monitoring of nuclear processes.

47 OTHER INSTRUMENTATION↗

COSMOLOGICAL EVOLUTION OF ATOMIC GAS AND IMPLICATIONS FOR 21 cm H I ABSORPTION

Galaxy disks are shown to contain a significant population of atomic clouds of 100 pc linear size which are self-opaque in the 21 cm transition. These objects have H I column densities as high as 10{sup 23} cm{sup -2} and contribute to a global opacity correction factor of 1.34 {+-} 0.05 that applies to the integrated 21 cm emission to obtain a total H I mass estimate. High-resolution, opacity-corrected images of the nearest external galaxies have been used to form a robust redshift zero distribution function of H I, f(N{sub HI}, X, z = 0), the probability of encountering a specific H I column density along random lines of sight per unit comoving distance. This is contrasted with previously published determinations of f(N{sub HI}, X) at z = 1 and 3. A systematic decline of moderate column density (18 < log(N{sub H)} < 21) H I is observed with decreasing redshift that corresponds to a decline in surface area of such gas by a factor of five since z = 3. The number of equivalent Damped Lyman Alpha absorbers (log(N{sub HI})>20.3) has also declined systematically over this redshift interval by a similar amount, while the cosmological mass density in such systems has declined by only a factor of two to its current, opacity-corrected value of {Omega}{sup DLA}{sub HI}(z = 0) = 5.4 {+-} 0.9 Multiplication-Sign 10{sup -4}. We utilize the tight but strongly nonlinear dependence of 21 cm absorption opacity on column density at z = 0 to transform our high-resolution H I images into ones of 21 cm absorption opacity. These images are used to calculate distribution and pathlength functions of integrated 21 cm opacity. We suggest that that this z = 0 calibration may also apply at higher redshift. In this case, the incidence of deep 21 cm absorption systems is predicted to show very little evolution with redshift, while that of faint absorbers should decline by a factor of 5 between z = 3 and the present. We explicitly consider the effects of H I absorption against background sources that are extended relative to the 100 pc intervening absorber size scale. Extended background sources result in dramatically altered distribution and pathlength functions which are insensitive to the predicted redshift evolution. Future surveys of 21 cm absorption will require very high angular resolution, of about 15 mas, for their unambiguous interpretation.

79 ASTRONOMY AND ASTROPHYSICS↗

Fugitive methane detection using open-path stand-off chirped laser dispersion spectroscopy

We report an open-path chirped laser dispersion spectrometer capable of detecting the atmospheric methane concentration above the background using both specular and diffusive reflective surfaces via two distinct operation modes in a stand-off detection configuration. The system is integrated with simultaneous ranging functionality, which enables average concentration measurements for varying optical pathlengths. The system was first tested for accuracy and characterized to achieve sensitivity of 2.9 p p m - m / H z 1 / 2 and pathlength precision of 0.2 m / H z 1 / 2 with a controlled release of methane outside the laboratory. The instrument was subsequently field-deployed in the proximity of a natural gas compressor station for fugitive methane detection. The instrument successfully detected methane plumes and narrowed down the location of the plume through multi-path measurement. The field measurements were verified by a co-located reference mobile methane sensor.

Chen, Yifeng↗

A Proposed Beam-Beam Test Facility COMBINE

The COmpact Machine for Beam-beam Interactions in Non-Equilibrium systems (COMBINE) is a proposed, dedicated, beam-beam test facility. This is currently a joint effort between Jefferson Lab and Old Dominion University to create a small, low energy pair of collider rings that would be used to study beam-beam interactions, as well as act as a teaching tool for students. The base design would make use of a pair of identical rings (2.5 meters per side) one rotated 180 degrees from the other, meeting at their common interaction point. These would be fed by an electron gun producing up to 125 keV electrons. The low energy will allow for beam-beam tune shifts commensurate with existing colliders, and will also allow for an exploration of the predicted effects of gear-changing, which would be performed using a variable pathlength scheme. Finally, this machine can also test linac-ring type systems.

Nissen, Edith↗

Design and Fabrication of a Precious Metal‐Free Tandem Core–Shell p + n Si/W‐Doped BiVO 4 Photoanode for Unassisted Water Splitting

Abstract Tandem photoelectrochemical water splitting cells utilizing crystalline Si and metal oxide photoabsorbers are promising for low‐cost solar hydrogen production. This study presents a device design and a scalable fabrication scheme for a tandem heterostructure photoanode: p + n black silicon (Si)/SnO 2 interface/W‐doped bismuth vanadate (BiVO 4 )/cobalt phosphate (CoPi) catalyst. The black‐Si not only provides a substantial photovoltage of 550 mV, but it also serves as a conductive scaffold to decrease charge transport pathlengths within the W‐doped BiVO 4 shell. When coupled with cobalt phosphide (CoP) nanoparticles as hydrogen evolution catalysts, the device demonstrates spontaneous water splitting without employing any precious metals, achieving an average solar‐to‐hydrogen efficiency of 0.45% over the course of an hour at pH 7. This fabrication scheme offers the modularity to optimize individual cell components, e.g., Si nanowire dimensions and metal oxide film thickness, involving steps that are compatible with fabricating monolithic devices. This design is general in nature and can be readily adapted to novel, higher performance semiconducting materials beyond BiVO 4 as they become available, which will accelerate the process of device realization.

Chakthranont, Pongkarn↗

Characterization of the external and internal flow structure of an aerated-liquid injector using X-ray radiography and fluorescence

In the present study, the internal flowfield of aerated-liquid fuel injectors is examined through x-ray radiography and x-ray fluorescence. An inside-out injector, consisting of a perforated aerating tube within an annular liquid stream, sprays into a quiescent environment at a fixed mass flow rate of water and nitrogen gas. The liquid is doped with bromine (in the form of NaBr) to create an x-ray fluorescence signal. This allows for reasonable absorption and fluorescence signals, and one or both diagnostics can be used to track the liquid distribution. The injector housing is fabricated from beryllium (Be), which allows the internal flowfield to be examined (as Be has relatively low x-ray attenuation coefficient). Two injector geometries are compared, illustrating the effects of aerating orifice size and location on the flow evolution. Time-averaged equivalent pathlength (EPL) and line-of-sight averaged density ρ(y) reveal the formation of the two-phase mixture, showing that the liquid film thickness along the injector walls is a function of the aerating tube geometry, though only upstream of the nozzle. These differences in gas and liquid distribution (between injectors with different aerating tube designs) are suppressed as the mixture traverses the nozzle contraction. The averaged liquid velocity (computed from the density and liquid mass flow rate) reveal a similar trend. This suggests that at least for the current configurations, the plume width, liquid mass distribution, and averaged liquid velocity for the time-averaged external spray are insensitive to the aerating tube geometry.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Stationary and drone-assisted methane plume localization with dispersion spectroscopy

This work presents stationary and mobile retroreflector-based remote sensing techniques for methane leak localization and quantification using chirped laser dispersion spectroscopy equipped with a custom laser transceiver capable of continuous tracking of a flying drone and coupled with inverse atmospheric gas dispersion modeling. The techniques demonstrate the ability to localize leaks as low as 0.13 g CH 4 ·s -1 , which are up to 25 times smaller than those typically observed at natural gas facilities, as well as actively track a moving retroreflector mounted on a lightweight (~250 g) drone to enable spatial plume reconstruction. This system exhibited a 2.3 ppm-m sensitivity over pathlengths of 40–150 m. Source localization to within ±7 m is demonstrated using a modified horizontal radial plume mapping technique with a stationary retroreflector grid. Meanwhile, the mobile system utilizing a drone-mounted retroreflector is able to localize a controlled release within ±1 m of its source location and estimate leak rates using inversion techniques assuming type B Gaussian plume stability class within ±30% error with respect to the actual low flow rate releases.

47 OTHER INSTRUMENTATION↗

Cyclable Variable Path Length Multilevel Structures for Lossless Ion Manipulations (SLIM) Platform for Enhanced Ion Mobility Separations

Ion mobility-mass spectrometry (IMS-MS) is increasingly used to analyze complex samples and provide structural information of unknown compounds. As the complexity of samples increases, there is a need to improve the resolution of IMS-MS instruments to increase the rate of molecular identification. In this work, we evaluated a cyclable and variable-pathlength multilevel Structures for Lossless Ion Manipulations (SLIM) platform to achieve a higher resolving power than previously possible. This new multilevel SLIM platform has eight separation levels connected by ion escalators and a path length of ~88 meters (~11 meters per level). Our new multilevel SLIM can also be operated in an ‘ion cycling’ mode where a set of return ion escalators transport ions from the eighth back to the first level, allowing even longer path lengths (and higher IMS resolution). The platform has been improved to enhance the ion transmission and IMS separation quality by reducing the spacing between SLIM boards as well as board thickness, reducing the ions’ escalator residence time. Compared to the previous generation, the new multilevel SLIM demonstrated a better transmission for a set of phosphazene ions, especially for the low-mobility ions. The new multilevel SLIM achieved better resolving powers than our previous 4-level SLIM. The collision cross-section-based resolving power of the SLIM platform was tested using a pair of singly-charged reverse sequence peptides (SDGRG 1+ , GRGDS 1+ ). We achieved 1100 resolving power using 88 meters of path length (i.e., 8 levels) and 1400 following an additional pass through the eight levels (i.e., 16 levels or 173.5 m). The multilevel SLIM was further evaluated to demonstrate the enhanced separation for a positively and negatively charged brain total lipid extract sample. Finally, the new multilevel SLIM enables much higher resolving powers for a wide range of ion mobilities, improved transmission for low-mobility ions, and the ability to perform even higher resolving power for ions of interest.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and Characterization of “Atlas-Sphere” Copper Nanoclusters: New Insights into the Reaction of Cu 2+ with Thiols

Thiolates are a widely used ligand class for the stabilization of M(0)-containing gold and silver nanoclusters. Curiously, though, very few thiolate-stabilized Cu nanoclusters are known. Herein, we report an examination of the reactivity of RSH (R = CH 2 CH 2 Ph, n-Bu, n-C 12 H 25 ) with Cu 2+ under anhydrous conditions. These reactions result in the formation of fluorescent "Atlas-sphere"-type copper thiolate nanoclusters, including [Cu 12 (SR') 6 Cl 12 ][(Cu(R'SH)) 6 ] (2, R' = n Bu) and [H(THF) 2 ] 2 [Cu 17 (SR'') 6 Cl 13 (THF) 2 (R''SH) 3 ] (3, R'' = CH 2 CH 2 Ph), which were characterized by X-ray crystallography, electrospray ionization mass spectrometry, NMR spectroscopy, as well as X-ray absorption near-edge structure and extended X-ray absorption fine structure (EXAFS) spectroscopies. Consistent with our X-ray crystallographic results, the edge energies of 2 and 3 suggest they are constructed exclusively with Cu(I) ions. Likewise, EXAFS of 2 and 3 reveals long Cu-Cu pathlengths, which is also consistent with their X-ray crystal structures. Given these results, as well as past work on Cu 2+ /thiol reactivity, we suggest that Cu(0) is unlikely to be formed by the reaction of Cu 2+ with a thiol and that previous reports of Cu(0)-containing nanoclusters synthesized by reaction of Cu 2+ with thiols are likely erroneous.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An Open-path Laser Transmissometer for Atmospheric Extinction Measurements

A transmissometer is an optical instrument which measures transmitted intensity of monochromatic light over a fixed pathlength. Prototype of a simple laser transmissometer has been developed for transmission (or extinction) measurements through suspended absorbers and scatterers in the atmosphere over tens of meters. Instrument consists of a continuous green diode pumped solid state laser, transmission optics, photodiode detectors and A/D data acquisition components. A modulated laser beam is transmitted and subsequently reflected and returned to the unit by a retroreflecting mirror assembly placed several tens of meters away. Results from an open-path field measurement of the instrument are described.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Observation of Infrared Free-Induction Decay and Optical Nutation Signals from Nitrous Oxide Using a Current Modulated Quantum Cascade Laser

Free induction decay (FID), optical nutation and rapid passage induced (RP) signals in nitrous oxide, under both optically thin and optically thick conditions, have been observed using a rapid current pulse modulation, or chirp, applied to the slow current ramp of a quantum cascade (QC) laser. The variation in optical depth was achieved by increasing the pressure of nitrous oxide in a long pathlength multipass absorption cell. This allows the variation of optical depth to be achieved over a range of low gas pressures. Since, even at the highest gas pressure used in the cell, the chirp rate of the QC laser is faster than the collisional reorientation time of the molecules, there is minimal collisional damping, allowing a large macroscopic polarization of the molecular dipoles to develop. This is referred to as rapid passage induced gain. The resultant FID signals are enhanced due to the constructive interference between the field within the gas generated by the slow ramp of the laser (pump), and the fast chirp of the laser (probe) signal generated by pulse modulation of the continuously operating QC laser. The FID signals obtained at large 2 optical depth have not been observed previously in the mid-infrared regions, and unusual oscillatory signals have been observed at the highest gas pressures used.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

THE COSMIC ORIGINS SPECTROGRAPH

The Cosmic Origins Spectrograph (COS) is a moderate-resolution spectrograph with unprecedented sensitivity that was installed into the Hubble Space Telescope (HST) in 2009 May, during HST Servicing Mission 4 (STS-125). We present the design philosophy and summarize the key characteristics of the instrument that will be of interest to potential observers. For faint targets, with flux F{sub {lambda}} Almost-Equal-To 1.0 Multiplication-Sign 10{sup -14} erg cm{sup -2} s{sup -1} A{sup -1}, COS can achieve comparable signal to noise (when compared to Space Telescope Imaging Spectrograph echelle modes) in 1%-2% of the observing time. This has led to a significant increase in the total data volume and data quality available to the community. For example, in the first 20 months of science operation (2009 September-2011 June) the cumulative redshift pathlength of extragalactic sight lines sampled by COS is nine times than sampled at moderate resolution in 19 previous years of Hubble observations. COS programs have observed 214 distinct lines of sight suitable for study of the intergalactic medium as of 2011 June. COS has measured, for the first time with high reliability, broad Ly{alpha} absorbers and Ne VIII in the intergalactic medium, and observed the He II reionization epoch along multiple sightlines. COS has detected the first CO emission and absorption in the UV spectra of low-mass circumstellar disks at the epoch of giant planet formation, and detected multiple ionization states of metals in extra-solar planetary atmospheres. In the coming years, COS will continue its census of intergalactic gas, probe galactic and cosmic structure, and explore physics in our solar system and Galaxy.

79 ASTRONOMY AND ASTROPHYSICS↗

An interpretation of flare-induced and decayless coronal-loop oscillations as interference patterns

We present an alternative model of coronal-loop oscillations, which considers that the waves are trapped in a two-dimensional waveguide formed by the entire arcade of field lines. This differs from the standard one-dimensional model which treats the waves as the resonant oscillations of just the visible bundle of field lines. Within the framework of our two-dimensional model, the two types of oscillations that have been observationally identified, flare-induced waves and 'decayless' oscillations, can both be attributed to MHD fast waves. The two components of the signal differ only because of the duration and spatial extent of the source that creates them. The flare-induced waves are generated by strong localized sources of short duration, while the decayless background can be excited by a continuous, stochastic source. Further, the oscillatory signal arising from a localized, short-duration source can be interpreted as a pattern of interference fringes produced by waves that have traveled diverse routes of various pathlengths through the waveguide. The resulting amplitude of the fringes slowly decays in time with an inverse square root dependence. The details of the interference pattern depend on the shape of the arcade and the spatial variation of the Alfvén speed. The rapid decay of this wave component, which has previously been attributed to physical damping mechanisms that remove energy from resonant oscillations, occurs as a natural consequence of the interference process without the need for local dissipation.

79 ASTRONOMY AND ASTROPHYSICS↗