Solid waste samples consisting of shredded cellulose, coated with either mesoparticles of metallic salts or dried metal nitrate (lutetium, ytterbium, or depleted uranium) solutions, were generated to mimic solid nuclear waste. After burning these samples, the masses of the aerosolized metal cations were quantified by leaching them from air filters and analyzing the leachate with inductively coupled plasma mass spectrometry. The airborne release fractions (ARFs) for Lu and depleted uranium nitrates were 1 x 10(-4), and 3 x 10(-3) for Lu and depleted uranium mesoparticle salts, respectively. Uncertainties in ARFs were approximately 10% for the metal nitrates and 30% for the metallic mesoparticles. These data are most applicable to waste materials with 1% metal mass loading where the initial respirable fraction of contaminant particles is one. ARFs were consistent across the two metals, but there was an order of magnitude difference with respect to the physical and chemical form (mesoparticle salt versus nitrate). Cellulose combustion literature indicates that combustion pathways were likely affected by off-gassing and endothermic decomposition reactions. In comparison to ARF values from DOE-HDBK-3010-94, "Airborne Release Fractions/Rates and Respirable Fractions for Nonreactor Nuclear Facilities," this dataset was consistent with previous results but provides a well-characterized and reproducible method for doping cellulosic materials with nuclear waste surrogates to serve as a baseline for future experimental and computational works.
The synthesis of a family of aluminum alkoxides was undertaken via the reaction of trimethyl aluminum (Al(CH3)(3)) using a series of sterically varied ortho-substituted phenols (H-OAr), including: 2-methyl phenol (H-oMP), 2-isopropyl phenol (H-oPP), 2-phenyl phenol (H-oPhP), 2,6-di-methyl phenol (H-DMP), 2,6-di-isopropyl phenol (H-DIP), and 2,6-di-phenyl phenol (H-DPhP). The products isolated using the least sterically encumbered phenoxides proved to generate the homoleptic compounds: [(oMP)Al((mu-oMP)(2)Al(oMP)(2))(2)] (1), and [Al(mu-oPP)(oPP)(2)](2) (2), [Al(mu-oPP)(oPP)(2)(THF)](2) (2-THF), and [Al(mu-oPhP)(oPhP)(2)](2) (3). As the steric bulk was increased only partial substitution was achieved forming the alkyl, alkoxide compounds: [Al(mu-OAr)(CH3)(OAr)](2) (OAr = trans-DMP (4a), cis-DIP (5a), trans-DPhP (6a)). Sub-stoichiometric metathesis reactions for the smaller OAr ligands were undertaken to produce a series of [Al(CH3)(3-x)(OAr)(x)](2) where x = 2: OAr = trans-oMP (1a); x = 1, OAr = oMP (1b), and DMP (4b). Alternatively, the use of neo-pentanol (H-ONep) led to the homoleptic species [(ONep)Al((mu-ONep)(2)Al(ONep)(2))(2)] (7) and heteroleptic [Al(mu-ONep)(CH3)(2)](2) (7b). Efforts to generate 7 from [Al(OPri)(3)](4) resulted in the production of the mixed ligated species [Al-4(mu-OPri)(6)(ONep)(6)] (8). The compounds were fully characterized using a variety of analytical tools as well as multinuclear NMR (H-1, C-13, Al-27) spectroscopy. Select species were used for aerosol spray pyrolysis for the anticipated production of alumina (Al2O3) materials. The final products from 1, 1b, 7, and 7b proved to generate amorphous mesoparticles of size 2.1(0.1), 2.6(0.2), 2.7(0.2), and 2.5(0.2) mu m, respectively as determined by SEM and pXRD analyses. Data collected using Single Particle Aerosol Mass Spectrometry (SPAMS) revealed that Al-0 particles had been produced instead of the expected Al2O3 ceramic materials.
Single particle aerosol mass spectrometry (SPAMS), an analytical technique for measuring the size and composition of individual micron-scale particles, is capable of analyzing atmospheric pollutants and bioaerosols much more efficiently and with more detail than conventional methods which require the collection of particles onto filters for analysis in the laboratory. Despite SPAMS' demonstrated capabilities, the primary mechanisms of ionization are not fully understood, which creates challenges in optimizing and interpreting SPAMS signals. In this paper, we present a well-stirred reactor model for the reactions involved with the laser-induced vaporization and ionization of an individual particle. The SPAMS conditions modeled in this paper include a 248 nm laser which is pulsed for 8 ns to vaporize and ionize each particle in vacuum. The ionization of 1 mu m, spherical Al particles was studied by approximating them with a 0-dimensional plasma chemistry model. The primary mechanism of absorption of the 248 nm photons was pressure-broadened direct photoexcitation to Al(y(2)D). Atoms in this highly excited state then undergo superelastic collisions with electrons, heating the electrons and populating the lower energy excited states. We found that the primary ionization mechanism is electron impact ionization of various excited state Al atoms, especially Al(y(2)D). Because the gas expands rapidly into vacuum, its temperature decreases rapidly. The rate of three-body recombination (e(-) + e(-) + Al+ -> Al + e(-)) increases at low temperature, and most of the electrons and ions produced recombine within several mu s of the laser pulse. The importance of the direct photoexcitation indicates that the relative peak heights of different elements in SPAMS mass spectra may be sensitive to the available photoexcitation transitions. The effects of laser intensity, particle diameter, and expansion dynamics are also discussed.
Abstract Airborne contaminants from fires containing nuclear waste represent significant health hazards and shape the design and operation of nuclear facilities. Much of the data used to formulate DOE-HDBK-3010-94, “Airborne Release Fractions/Rates and Respirable Fractions for Nonreactor Nuclear Facilities,” from the U.S. Department of Energy, were taken over 40 years ago. The objectives of this study were to reproduce experiments from Pacific Northwest Laboratories conducted in June 1973 employing current aerosol measurement methods and instrumentation, develop an enhanced understanding of particulate formation and transport from fires containing nuclear waste, and provide modeling and experimental capabilities for updating current standards and practices in nuclear facilities. A special chamber was designed to conduct small fires containing 25 mL of flammable waste containing lutetium nitrate, ytterbium nitrate, or depleted uranium nitrate. Carbon soot aerosols showed aggregates of primary particles ranging from 20 to 60 nm in diameter. In scanning electron microscopy, ~200-nm spheroidal particles were also observed dispersed among the fractal aggregates. The 200-nm spherical particles were composed of metal phosphates. Airborne release fractions (ARFs) were characterized by leaching filter deposits and quantifying metal concentrations with mass spectrometry. The average mass-based ARF for 238U experiments was 1.0 × 10−3 with a standard deviation of 7.5 × 10−4. For the original experiments, DOE-HDBK-3010-94 states, “Uranium ARFs range from 2 × 10−4 to 3 × 10−3, an uncertainty of approximately an order of magnitude.” Thus, current measurements were consistent with DOE-HDBK-3010-94 values. ARF values for lutetium and ytterbium were approximately one to two orders of magnitude lower than 238U. Metal nitrate solubility may have varied with elemental composition and temperature, thereby affecting ARF values for uranium surrogates (Yb and Lu). In addition to ARF data, solution boiling temperatures and evaporation rates can also be deduced from experimental data.
a 4{omega} probe beam. This enabled sub- and super- critical densities to be probed relative to the 1{omega} heater beams. The deduced plasma hydrodynamic conditions are compared with those generated from the 1-D hydro-code Medusa, and the significant differences found in the electron temperature discussed. Synthetic spectra generated from the detailed term collisional radiative non-LTE atomic physics code Fly are compared with the experimental spectra for the measured hydrodynamic parameters, and for those taken from Medusa. Excellent agreement is only found for both the H- and He-like Al series when careful account is taken of the temporal evolution of the electron temperature.
evaluated. The LAS-X is relatively insensitive to changes in aerosol concentration and refractive index over the range of interest for filter testing. It appears that the LAS-X would provide a better instrument for monitoring aerosol size, and would permit the FTF test operator to adjust the test aerosol to approximate the size characteristics currently recommended for this test.
Two material types identified by Sew-EZ were tested in various configurations, and under various conditions, by Sandia National Laboratories (SNL). The primary focus of this study was to assess the filtration performance of these two materials and identify if they perform similarly to certified N95 respirators. Testing was conducted on two systems which use distinctly different techniques to characterize the aerosol penetration characteristics of materials: a) R&D Filtration System: A large-scale R&D filtration system was used with testing parameters that mimicked NIOSH guidelines, where possible. Efficiency data as a function of particle size was attained using NaC1 as the test aerosol and a Scanning Mobility Particle Sizer (SMPS) for measurements. A more detailed system description can be found in Omana et al. 2020. b) Automated Tester: A commercial, automated filter tester (100Xs, Air Techniques International) was used to provide penetration/efficiency data for Sew EZ materials. The 100Xs aerosolizes a polydisperse NaC1 aerosol with a consistent concentration and size profile. The 100Xs manual (Air Techniques International 2018) states, "The aerosol particle size and distribution are designed to meet all requirements as defined in the relevant sections of NIOSH 42 CFR, Part 84 (pg. 32)."
Sandia National Laboratories (SNL) assessed the filtration performance of materials from Sierra Peaks to identify alternatives which may perform similarly to materials used in FDA-approved N95 respirators. This work is meant to characterize the aerosol performance of materials to give Sierra Peaks information for them to determine if they elect to submit masks made using these materials for follow-on N95 certification testing at an accredited facility. The R&D testbed used is a large-scale filtration system designed to test commercial filter boxes. System modifications were performed to simulate, where possible, parameters defined by the National Institute for Occupational Safety and Health (NIOSH) for certification of filter materials for N95 respirators (NIOSH 2019). The system is a pull-through design. Air enters through a Laminar Flow Element (LFE) and the volumetric flow is measured based on the pressure drop across the LFE. Pressure is measured via a Pressure Transducer (PT). The air then passes through a High Efficiency Particulate Air (HEPA) filter to purge the air of ambient airborne particulates. Test aerosol is injected into the flow shortly after and mixing is induced via a coarse mesh. The airflow is allowed to fully develop prior to arriving at the test section. The aerosol then passes through the test material mounted in a box in the test section. Pressure drop across the test article is measured and aerosol sampling probes measure the aerosol concentrations upstream and downstream of the sample. The air passes through a second HEPA filter prior to being exhausted to ambient by a blower. A Topas aerosol generator is used to produce the test aerosol from Sodium Chloride (NaC1) dissolved in deionized (DI) water. Generated aerosol passes through a heated mixing chamber and a desiccant dryer to produce nanosized solid-state particulates. A dilution loop allows for the aerosol concentration to be regulated. The aerosol sampling probes upstream and downstream of the test section are aligned with the flow path. These are ducted directly to the aerosol sizing and counting instruments. A Laser Aerosol Spectrometer (LAS) was used for data collection in the original configuration of the system and was also used for initial testing in this project. Because the lower measurement range for the LAS is 90 nanometers (nm), the LAS was switched out for a more complicated Scanning Mobility Particle Sizer (SMPS) spectrometer system. The SMPS is comprised of an Electrostatic Classifier (EC), Differential Mobility Analyzer (DMA), and a Condensation Particle Counter (CPC). This enabled data collection at 75 nm, the particle size called out in the NIOSH guidelines.
A vaccine for smallpox is no longer administered to the general public, and there is no proven, safe treatment specific to poxvirus infections, leaving people susceptible to infections by smallpox and other zoonotic Orthopoxviruses such as monkeypox. Using vaccinia virus (VACV) as a model organism for other Orthopoxviruses, CRISPR–Cas9 technology was used to target three essential genes that are conserved across the genus, including A17L, E3L, and I2L. Three individual single guide RNAs (sgRNAs) were designed per gene to facilitate redundancy in rendering the genes inactive, thereby reducing the reproduction of the virus. The efficacy of the CRISPR targets was tested by transfecting human embryonic kidney (HEK293) cells with plasmids encoding both SaCas9 and an individual sgRNA. This resulted in a reduction of VACV titer by up to 93.19% per target. Following the verification of CRISPR targets, safe and targeted delivery of the VACV CRISPR antivirals was tested using adeno-associated virus (AAV) as a packaging vector for both SaCas9 and sgRNA. Similarly, AAV delivery of the CRISPR antivirals resulted in a reduction of viral titer by up to 92.97% for an individual target. Overall, we have identified highly specific CRISPR targets that significantly reduce VACV titer as well as an appropriate vector for delivering these CRISPR antiviral components to host cells in vitro.