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Preliminary Effects of Real-World Factors on the Recovery and Exploitation of Forensic Impurity Profiles of a Nerve-Agent Simulant from Office Media

Dimethyl methylphosphonate (DMMP) was used as a chemical threat agent (CTA) simulant for a first look at the effects of real-world factors on the recovery and exploitation of a CTA’s impurity profile for source matching. Four stocks of DMMP having different impurity profiles were disseminated as aerosols onto cotton, painted wall board, and nylon coupons according to a thorough experimental design. The DMMP-exposed coupons were then solvent extracted and analyzed for DMMP impurities by comprehensive 2-D gas chromatography/mass spectrometry (GC×GC/MS). The similarities between the coupon DMMP impurity profiles and the known (reference) DMMP profiles were measured by dot products of the coupon profiles and known profiles and by score values obtained from principal component analysis. One stock, with a high impurity-profile selectivity value of 0.9 out of 1, had 100% of its respective coupons correctly classified and no false positives from other coupons. Coupons from the other three stocks with low selectivity values (0.0073, 0.012, and 0.018) could not be sufficiently distinguished from one another for reliable matching to their respective stocks. The results from this work support that: (1) extraction solvents, if not appropriately selected, can have some of the same impurities present in a CTA reducing a CTA’s useable impurity profile, (2) low selectivity among a CTA’s known impurity profiles will likely make definitive source matching impossible in some real-world conditions, (3) no detrimental chemical-matrix interference was encountered during the analysis of actual office media, (4) a short elapsed time between release and sample storage is advantageous for the recovery of the impurity profile because it minimizes volatilization of forensic impurities, and (5) forensic impurity profiles weighted towards higher volatility impurities are more likely to be altered by volatilization following CTA exposure.

Chemical forensics↗

WE-EF-207-09: Single-Scan Dual-Energy CT Using Primary Modulation

Purpose: Compared with conventional CT, dual energy CT (DECT) provides better material differentiation but requires projection data with two different effective x-ray spectra. Current DECT scanners use either a two-scan setting or costly imaging components, which are not feasible or available on open-gantry cone-beam CT systems. We propose a hardware-based method which utilizes primary modulation to enable single-scan DECT on a conventional CT scanner. The CT imaging geometry of primary modulation is identical to that used in our previous method for scatter removal, making it possible for future combination with effective scatter correction on the same CT scanner. Methods: We insert an attenuation sheet with a spatially-varying pattern - primary modulator-between the x-ray source and the imaged object. During the CT scan, the modulator selectively hardens the x-ray beam at specific detector locations. Thus, the proposed method simultaneously acquires high and low energy data. High and low energy CT images are then reconstructed from projections with missing data via an iterative CT reconstruction algorithm with gradient weighting. Proof-of-concept studies are performed using a copper modulator on a cone-beam CT system. Results: Our preliminary results on the Catphan(c) 600 phantom indicate that the proposed method for single-scan DECT is able to successfully generate high-quality high and low energy CT images and distinguish different materials through basis material decomposition. By applying correction algorithms and using all of the acquired projection data, we can reconstruct a single CT image of comparable image quality to conventional CT images, i.e., without primary modulation. Conclusion: This work shows great promise in using a primary modulator to perform high-quality single-scan DECT imaging. Future studies will test method performance on anthropomorphic phantoms and perform quantitative analyses on image qualities and DECT decomposition accuracy. We will use simulations to optimize the modulator material and geometry parameters.

60 APPLIED LIFE SCIENCES↗

A selection function toolbox for subsets of astronomical catalogues

ABSTRACT Large catalogues are ubiquitous throughout astronomy, but most scientific analyses are carried out on smaller samples selected from these catalogues by chosen cuts on catalogued quantities. The selection function of that scientific sample – the probability that a star in the catalogue will satisfy these cuts and so make it into the sample – is thus unique to each scientific analysis. We have created a general framework that can flexibly estimate the selection function of a sample drawn from a catalogue in terms of position, magnitude and colour. Our method is unique in using the binomial likelihood and accounting for correlations in the selection function across position, magnitude, and colour using Gaussian processes and spherical harmonics. We have created a new open-source python package selectionfunctiontoolbox that implements this framework and used it to make three different estimates of the APOGEE DR16 red giant sample selection function, as a subset of 2MASS, with each estimate using an increasing amount of technical knowledge of the APOGEE targeting. In a companion paper, we applied our methodology to derive estimates of the astrometric and spectroscopic selection functions of Gaia EDR3. Our framework will make it trivial for astrophysicists to estimate the selection function that they should be using with the custom sample of stars that they have chosen to answer their scientific question.

79 ASTRONOMY AND ASTROPHYSICS↗

Review Article: Advanced nanoscale patterning and material synthesis with gas field helium and neon ion beams

Focused ion beam nanoscale synthesis has emerged as a critical tool for selected area nanofabrication. Helium and neon ion beams from the gas field ion source have recently demonstrated unparalleled resolution among other scanning ion beams. In this review, the authors focus on the nanoscale synthesis applications for these ion species which have been demonstrated to date. The applications and recent work can broadly be grouped into the following categories: (1) Monte Carlo simulations, (2) direct-write milling or sputtering, (3) ion beam lithography, (4) selective ion implantation or defect introduction, and (5) gas-assisted processing. A special emphasis is given toward using He+ and Ne+ for the processing of two dimensional materials, as several groups have demonstrated promising results. Finally, the authors will discuss the future outlook of He+ and Ne+ nanoprocessing techniques and applications.

Stanford, Michael G.↗

New associations of gamma-ray sources from the Fermi second source catalog

We present the results of an all-sky radio survey between 5 and 9 GHz of sky areas surrounding all unassociated γ-ray objects listed in the Fermi Large Area Telescope Second Source Catalog (2FGL). The goal of these observations is to find all new γ-ray active galactic nucleus (AGN) associations with radio sources >10 mJy at 8 GHz. We observed with the Very Large Array and the Australia Telescope Compact Array the areas around unassociated sources, providing localizations of weak radio point sources found in 2FGL fields at arcmin scales. Then we followed-up a subset of those with the Very Long Baseline and the Long Baseline Arrays to confirm detections of radio emission on parsec-scales. We quantified association probabilities based on known statistics of source counts and assuming a uniform distribution of background sources. In total we found 865 radio sources at arcsec scales as candidates for association and detected 95 of 170 selected for follow-up observations at milliarcsecond resolution. Based on this we obtained firm associations for 76 previously unknown γ-ray AGNs. Comparison of these new AGN associations with the predictions from using the Wide-field Infrared Survey Explorer color–color diagram shows that half of the associations are missed. We found that 129 out of 588 observed γ-ray sources at arcmin scales not a single radio continuum source was detected above our sensitivity limit within the 3σ γ-ray localization. These “empty” fields were found to be particularly concentrated at low Galactic latitudes. The nature of these Galactic γ-ray emitters is not yet determined.

79 ASTRONOMY AND ASTROPHYSICS↗

Role of H 2 O in Catalytic Conversion of C 1 Molecules

Due to their role in controlling global climate change, the selective conversion of C 1 molecules such as CH 4 , CO, and CO 2 has attracted widespread attention. Typically, H 2 O competes with the reactant molecules to adsorb on the active sites and therefore inhibits the reaction or causes catalyst deactivation. However, H 2 O can also participate in the catalytic conversion of C 1 molecules as a reactant or a promoter. Herein, we provide a perspective on recent progress in the mechanistic studies of H 2 O-mediated conversion of C 1 molecules. We aim to provide an in-depth and systematic understanding of H 2 O as a promoter, a proton-transfer agent, an oxidant, a direct source of hydrogen or oxygen, and its influence on the catalytic activity, selectivity, and stability. We also summarize strategies for modifying catalysts or catalytic microenvironments by chemical or physical means to optimize the positive effects and minimize the negative effects of H 2 O on the reactions of C 1 molecules. Finally, we discuss challenges and opportunities in catalyst design, characterization techniques, and theoretical modeling of the H 2 O-mediated catalytic conversion of C 1 molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mass-selected ion–molecule cluster beam apparatus for ultrafast photofragmentation studies

We describe an apparatus for investigating the excited-state dissociation dynamics of mass-selected ion–molecule clusters by mass-resolving and detecting photofragment-ions and neutrals, in coincidence, using an ultrafast laser operating at high repetition rates. The apparatus comprises a source that generates ion–molecule clusters, a time-of-flight spectrometer, and a mass filter that selects the desired anions, and a linear-plus-quadratic reflectron mass spectrometer that discriminates the fragment anions after the femtosecond laser excites the clusters. The fragment neutrals and anions are then captured by two channeltron detectors. The apparatus performance is tested by measuring the photofragments: I – , CF 3 I – , and neutrals from photoexcitation of the ion–molecule cluster CF 3 I·I – using femtosecond UV laser pulses with a wavelength of 266 nm. Here, the experimental results are compared with our ground state and excited state electronic structure calculations as well as the existing results and calculations, with particular attention to the generation mechanism of the anion fragments and dissociation channels of the ion–molecule cluster CF 3 I·I – in the charge-transfer excited state.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Rovibrationally selected ion-molecule collision study using the molecular beam vacuum ultraviolet laser pulsed field ionization-photoion method: Charge transfer reaction of N{sub 2}{sup +}(X {sup 2}{Sigma}{sub g}{sup +}; v{sup +}= 0-2; N{sup +}= 0-9) + Ar

We have developed an ion-molecule reaction apparatus for state-selected absolute total cross section measurements by implementing a high-resolution molecular beam vacuum ultraviolet (VUV) laser pulsed field ionization-photoion (PFI-PI) ion source to a double-quadrupole double-octopole ion-guide mass spectrometer. Using the total cross section measurement of the state-selected N{sub 2}{sup +}(v{sup +}, N{sup +}) + Ar charge transfer (CT) reaction as an example, we describe in detail the design of the VUV laser PFI-PI ion source used, which has made possible the preparation of reactant N{sub 2}{sup +}(X {sup 2}{Sigma}{sub g}{sup +}, v{sup +}= 0-2, N{sup +}= 0-9) PFI-PIs with high quantum state purity, high intensity, and high kinetic energy resolution. The PFI-PIs and prompt ions produced in the ion source are shown to have different kinetic energies, allowing the clean rejection of prompt ions from the PFI-PI beam by applying a retarding potential barrier upstream of the PFI-PI source. By optimizing the width and amplitude of the pulsed electric fields employed to the VUV-PFI-PI source, we show that the reactant N{sub 2}{sup +} PFI-PI beam can be formed with a laboratory kinetic energy resolution of {Delta}E{sub lab}={+-} 50 meV. As a result, the total cross section measurement can be conducted at center-of-mass kinetic energies (E{sub cm}'s) down to thermal energies. Absolute total rovibrationally selected cross sections {sigma}(v{sup +}= 0-2, N{sup +}= 0-9) for the N{sub 2}{sup +}(X {sup 2}{Sigma}{sub g}{sup +}; v{sup +}= 0-2, N{sup +}= 0-9) + Ar CT reaction have been measured in the E{sub cm} range of 0.04-10.0 eV, revealing strong vibrational enhancements and E{sub cm}-dependencies of {sigma}(v{sup +}= 0-2, N{sup +}= 0-9). The thermochemical threshold at E{sub cm}= 0.179 eV for the formation of Ar{sup +} from N{sub 2}{sup +}(X; v{sup +}= 0, N{sup +}) + Ar was observed by the measured {sigma}(v{sup +}= 0), confirming the narrow {Delta}E{sub cm} spread achieved in the present study. The {sigma}(v{sup +}= 0-2; N{sup +}) values obtained here are compared with previous experimental and theoretical results. The theoretical predictions calculated based on the Landau-Zener-Stueckelberg formulism are found to be in fair agreement with the present measured {sigma}(v{sup +}= 1 or 2; N{sup +}). Taking into account of the experimental uncertainties, the measured {sigma}(v{sup +}= 1 or 2, N{sup +}) for N{sup +}= 0-9 at E{sub cm}= 0.04-10.0 eV are found to be independent of N{sup +}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Selective collection of iron-rich dust particles by natural Trichodesmium colonies

Abstract Dust is an important iron (Fe) source to the ocean, but its utilization by phytoplankton is constrained by rapid sinking and slow dissolution dust-bound iron (dust-Fe). Colonies of the globally important cyanobacterium, Trichodesmium, overcome these constraints by efficient dust capturing and active dust-Fe dissolution. In this study we examined the ability of Trichodesmium colonies to maximize their Fe supply from dust by selectively collecting Fe-rich particles. Testing for selectivity in particle collection, we supplied ~600 individual colonies, collected on multiple days from the Gulf of Aqaba, with natural dust and silica minerals that were either cleaned of or coated with Fe. Using a stereoscope, we counted the number of particles retained by each colony shortly after addition and following 24 h incubation with particles, and documented translocation of particles to the colony core. We observed a strong preference for Fe-rich particles over Fe-free particles in all tested parameters. Moreover, some colonies discarded the Fe-free particles they initially collected. The preferred collection of Fe-rich particles and disposal of Fe-free particles suggest that Trichodesmium can sense Fe and selectively choose Fe-rich dust particles. This ability assists Trichodesmium obtain Fe from dust and facilitate its growth and subsequent contribution to nutrient cycling and productivity in the ocean.

54 ENVIRONMENTAL SCIENCES↗

Engineering Yarrowia lipolytica for poly-3-hydroxybutyrate production

In this study, strains of Yarrowia lipolytica were engineered to express the poly-3-hydroxybutyrate (PHB) biosynthetic pathway. The genes for β-ketothiolase, NADPH-dependent acetoacetyl-CoA reductase, and PHB synthase were cloned and inserted into the chromosome of Y. lipolytica. In shake flasks, the engineered strain accumulated PHB to 1.50 and 3.84% of cell dry weight in complex medium supplemented with glucose and acetate as carbon source, respectively. In fed-batch fermentation using acetate as sole carbon source, 7.35 g/l PHB (10.2% of cell dry weight) was produced. Selection of Y. lipolytica as host for PHB synthesis was motivated by the fact that this organism is a good lipids producer, which suggests robust acetyl-CoA supply also the precursor of the PHB pathway. Lastly, acetic acid could be supplied by gas fermentation, anaerobic digestion, and other low-cost supply route.

59 BASIC BIOLOGICAL SCIENCES↗

Tritium permeability measurement in hydrogen-tritium system

Fusion power promises to provide electricity generation with outstanding safety and environmental performance. Safety plays a crucial role in fusion material selection since tritium behavior in materials determines two key safety evaluation source terms: in-vessel inventory source term and ex-vessel release term, which are used in reactor safety assessments for licensing fusion facilities. Tritium permeation through materials at elevated temperature during long pulse operation expected in a burning plasma environment will become a major safety issue and development of tritium permeation barrier materials is required to minimize ex-vessel release to the environment [1]. Extensive work on hydrogen and deuterium behavior in fusion materials has been conducted, but very little database is available for tritium, the radioactive fuel for future reactors, due to the cost and difficulty associated with handling tritium [2]. A majority of the experiments were carried out at high hydrogen/deuterium partial pressure (> 100 Pa), but the expected tritium partial pressure in the blanket system is at low tritium partial pressure (< 100 Pa), where the tritium behavior deviates from diffusion-limited to surface-limited permeation. At these pressures the behavior of tritium is suspected to deviate from diffusion-limited to surface-limited permeation or isotope-limited [3]. The use of tritium enables us to investigate hydrogen isotope behavior in low partial pressure range with beta radiation detection. The physics of two-component hydrogen (H+T) permeation through metal in the surface-limited regime and through liquid breeding material are still too poorly understood to confidently design environmentally benign and safe fusion systems. In this paper, we discuss development of tritium permeation system for low tritium partial pressure [4], and discuss the results from two-component hydrogen (H+T) permeation in 20 mm disc samples of pure alpha-iron at H2 partial pressure of 100 Pa, wide T2 partial pressure range from 10-12 to 10 Pa, and sample temperature up to 600 °C to uncover the basic scientific understanding of tritium permeation behavior at realistic blanket conditions for DEMO. [1] FESAC report on “Opportunities for Fusion Materials Science and Technology Research Now and During the ITER Era” (2012) DOE/SC-0149 [2] R.A. Causey, R.A. Karnesky, and C. San Marchi, “4.16 Tritium Barriers and Tritium Diffusion in Fusion Reactors”, Comprehensive Nuclear Materials (2012) Chapter 4.16. [3] P. Humrickhouse “Permeation of Tritium and Hydrogen in the Diffusion-Limited and Surface–Limited Regimes”, submitted to Journal of Nuclear Materials. [4] R.J. Pawelko, M. Shimada, K. Katayama, S. Fukada, P.W. Humrickhouse, and T. Terai, “Low tritium partial pressure permeation system for mass transport measurement in lead lithium eutectic”, Fusion Engineering and Design 102 (2016) 8

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Development of the hybrid sulfur cycle for use with concentrated solar heat. I. Conceptual design

We propose a detailed conceptual design of a solar hybrid sulfur (HyS) cycle. Numerous design tradeoffs, including process operating conditions and strategies, methods of integration with solar energy sources, and solar design options were considered. A baseline design was selected, and process flowsheets were developed. Pinch analyses were performed to establish the limiting energy efficiency. Detailed material and energy balances were completed, and a full stream table prepared. Design assumptions include use of: location in the southwest US desert, falling particle concentrated solar receiver, indirect heat transfer via pressurized helium, continuous operation with thermal energy storage, liquid-fed electrolyzer with PBI membrane, and bayonet-type acid decomposer. Thermochemical cycle efficiency for the HyS process was estimated to be 35.0%, LHV basis. The solar-to-hydrogen (STH) energy conversion ratio was 16.9%. This thus exceeds the Year 2015 DOE STCH target of STH >10%, and shows promise for meeting the Year 2020 target of 20%.

08 HYDROGEN↗

Selectively accessing the hotspots of optical nanoantennas by self-aligned dry laser ablation

Plasmonic nanostructures serve as optical antennas for concentrating the energy of incoming light in localized hotspots close to their surface. By positioning nanoemitters in the antenna hotspots, energy transfer is enabled, leading to novel hybrid antenna-emitter-systems, where the antenna can be used to manipulate the optical properties of the nano-objects. The challenge remains how to precisely position emitters within the hotspots. We report a self-aligned process based on dry laser ablation of a calixarene that enables the attachment of molecules within the electromagnetic hotspots at the tips of gold nanocones. Within the laser focus, the ablation threshold is exceeded in nanoscale volumes, leading to selective access of the hotspot areas. A first indication of the site-selective functionalization process is given by attaching fluorescently labelled proteins to the nanocones. In a second example, Raman-active molecules are selectively attached only to nanocones that were previously exposed in the laser focus, which is verified by surface enhanced Raman spectroscopy. Enabling selective functionalization is an important prerequisite e.g. for preparing single photon sources for quantum optical technologies, or multiplexed Raman sensing platforms.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Hypervelocity nanoparticle impacts on free-standing graphene: A sui generis mode of sputtering

The study of the interaction of hypervelocity nano-particles with a 2D material and ultra-thin targets (single layer graphene, multi-layer graphene, and amorphous carbon foils) has been performed using mass selected gold nano-particles produced from a liquid metal ion source. During these impacts, a large number of atoms are ejected from the graphene, corresponding to a hole of ∼60 nm{sup 2}. Additionally, for the first time, secondary ions have been observed simultaneously in both the transmission and reflection direction (with respect to the path of the projectile) from a 2D target. The ejected area is much larger than that predicted by molecular dynamic simulations and a large ionization rate is observed. The mass distribution and characteristics of the emitted secondary ions are presented and offer an insight into the process to produce the large hole observed in the graphene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation of negative ion distribution changes by image processing diagnostic

Distributions of hydrogen Balmer-α (H{sub α}) intensity and its reduction behavior close to a plasma grid (PG) surface have been observed by a spectrally selective imaging system in an arc discharge type negative hydrogen ion source in National Institute for Fusion Science. H{sub α} reduction indicates a reduction of negative hydrogen ions because the mutual neutralization process between H{sup +} and H{sup −} ions causes the dominant excitation process for H{sub α} emission in the rich H{sup −} condition such as in ionic plasma. We observed a significant change in H{sub α} reduction distribution due to change in the bias voltage, which is used to suppress the electron influx. Small H{sub α} reduction in higher bias is likely because the production of negative ions is suppressed by the potential difference between the plasma and PG surface.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

A compact and low-weight sputtering unit for in situ investigations of thin film growth at synchrotron radiation beamlines

In this work, we report on a highly variable, compact, and light high-vacuum sputter deposition unit designed for in situ experiments using synchrotron radiation facilities. The chamber can be mounted at various synchrotron beamlines for scattering experiments in grazing incidence geometry. The sample position and the large exit window allow to perform x-ray experiments up to large q values. The sputtering unit is easy to mount on existing experimental setups and can be remote-controlled. In this paper, we describe in detail the design and the performance of the new sputtering chamber and present the installation of the apparatus at different 3rd generation light sources. Furthermore, we describe the different measurement options and present some selected results. The unit has been successfully commissioned and is now available for users at PETRA III at DESY.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Assessment of Activation on Level L3 of the Tokamak Building due to the ITER Tokamak Cooling Water System

The ITER fusion reactor is being built to demonstrate the feasibility of fusion power and will be the largest tokamak in the world. The tokamak cooling water system (TCWS) will extract the heat generated during operations and includes large amounts of piping and equipment such as pumps and heat exchangers (HXs) that are located in a large shielded region on level L3 of the tokamak building. During operation, water in the TCWS will be activated by plasma neutrons and then flow into this shielded region. The activated coolant will in turn activate the steel in the TCWS during operation and result in an activation gamma source and radiation responses that must be assessed to inform equipment selection and maintenance schedules.The activation of materials in the shielded region of level L3 was assessed at several decay times and for different equipment options using the Oak Ridge National Laboratory (ORNL) shutdown dose rate (SDDR) code suite. The ORNL SDDR code suite implements the rigorous two-step method using the Multi-Step Consistent Adjoint-Driven Importance Sampling (MS-CADIS) method to create effective neutron variance reduction parameters for the photon response of interest. In conclusion, two different HX designs, shell and tube and shell and plate, were considered, as well as the impact of cobalt impurities in steel equipment.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

SPECTRAL CLASSIFICATION OF GALAXIES AT 0.5 {<=} z {<=} 1 IN THE CDFS: THE ARTIFICIAL NEURAL NETWORK APPROACH

The aim of this work is to combine spectral energy distribution (SED) fitting with artificial neural network techniques to assign spectral characteristics to a sample of galaxies at 0.5 < z < 1. The sample is selected from the spectroscopic campaign of the ESO/GOODS-South field, with 142 sources having photometric data from the GOODS-MUSIC catalog covering bands between {approx}0.4 and 24 {mu}m in 10-13 filters. We use the CIGALE code to fit photometric data to Maraston's synthesis spectra to derive mass, specific star formation rate, and age, as well as the best SED of the galaxies. We use the spectral models presented by Kinney et al. as targets in the wavelength interval {approx}1200-7500 A. Then a series of neural networks are trained, with average performance {approx}90%, to classify the best SED in a supervised manner. We consider the effects of the prominent features of the best SED on the performance of the trained networks and also test networks on the galaxy spectra of Coleman et al., which have a lower resolution than the target models. In this way, we conclude that the trained networks take into account all the features of the spectra simultaneously. Using the method, 105 out of 142 galaxies of the sample are classified with high significance. The locus of the classified galaxies in the three graphs of the physical parameters of mass, age, and specific star formation rate appears consistent with the morphological characteristics of the galaxies.

79 ASTRONOMY AND ASTROPHYSICS↗