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At least 199 records · Page 11

Retaining Geochemical Signatures during Aragonite-Calcite Transformation at Hydrothermal Conditions

Transformation of aragonite, a mineral phase metastable at Earth’s surface, to calcite widely occurs in both sedimentary and metamorphic systems with the presence of an aqueous phase. The transformation process can affect geochemical signatures of aragonite (a protolith). This study focused on quantification of the retention of Mg/Ca and Sr/Ca ratios, and δ18O during the transformation process as well as evaluation of the transformation rate. To investigate the effect of transformation from aragonite to calcite on elemental and stable isotope ratios, we conducted a series of experiments in NaCl solutions at temperatures between 120 and 184 °C. Two additional experiments at 250 °C were conducted to estimate the transformation rate of aragonite to calcite. Protolith materials consist of (1) synthetic (Mg; Sr-bearing or non-Mg; Sr bearing) needle-shaped microcrystals of aragonite (<5 µm in size) and (2) larger chips (>100 µm in size) of natural aragonite. X-ray diffraction (XRD) showed that microcrystals successfully transformed to calcite within 30 h and scanning electron microscopy (SEM) yielded a change in the crystal size to >10 µm in rhombohedral shape. Electron backscatter diffraction (EBSD) of the larger aragonite chips showed that transformation to randomly oriented calcite occurred at the rims and along the cracks while the core retained an aragonite crystal structure. Isotope-ratio mass spectrometry (IRMS) analyses showed that calcite δ18O was controlled by temperature and δ18O of the solution. The obtained calibration curve of isotope fractionation factor versus temperature is consistent with other studies. Inductively coupled plasma optical emission spectroscopy (ICP-OES) analyses showed that calcite partially or completely retained Mg/Ca and Sr/Ca ratios through the transformation.

58 GEOSCIENCES↗

Magnetic Sorbent for the Removal of Selenium(IV) from Simulated Industrial Wastewaters: Determination of Column Kinetic Parameters

A novel meso- and microporous tire-derived-carbon support with magnetic iron oxide nanoparticle adsorbents that selectively adsorbs Se(IV) ions from simulated contaminated water has been developed. In this work, the physicochemical characteristics of the composite adsorbent are characterized with respect to porosity and surface area, chemical composition, and microstructure morphology. The kinetics of this composite adsorbent in a fixed-bed setting has been determined. Several column runs were conducted and analyzed by inductively coupled plasma-optical emission spectroscopy (ICP-OES) to determine the concentration gradient vs time. These results were then fit to a pseudo-second order rate law to obtain equilibrium values. Combining calculated equilibrium values with effluent concentration data, enabled the application of the Adams–Bohart model to determine reaction constants and column coefficients. Column parameters obtained from different flow rates and fittings of the Adams–Bohart model were remarkably consistent. These findings enable the application of this sorbent to fixed-bed column systems and opens up further research into mixed pollutants tests with real wastewater and scaling of selenium pollutant removal.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nonoxidative dehydrogenation of propane using boron-incorporated silica-supported Pt Sites synthesized by atomic layer deposition

Nonoxidative dehydrogenation of propane to propylene using Pt-based supported catalysts is an active research area in catalysis because catalyst attributes of Pt sites can be controlled by careful design of active sites. One way to achieve this is by the addition of a second metal that may impart a change in the electron density of active sites, which in turn affects catalytic performance. In this study, bimetallic Pt and B sites were deposited on powder SiO2 using atomic layer deposition (ALD). Boron was first deposited on SiO2 via half-cycle ALD using triisoproplyborate as the B source. Following calcination, Pt deposition was performed via half-cycle ALD using trimethyl(methylcyclopentadienyl)platinum(IV) as the Pt source. The synthesized catalysts were reduced under H2 at 550 °C and characterized using inductively coupled plasma optical emission spectroscopy for elemental analysis, diffuse reflectance infrared Fourier transform spectroscopy of adsorbed CO to examine the properties of Pt, and time-resolved X-ray absorption near edge structure spectroscopy to examine the changes in the reducibility of Pt sites. The samples were then tested for nonoxidative dehydrogenation of propane at 550 °C using a fixed-bed plug-flow reactor to examine the role of B on the catalytic performance. Characterization results showed that the addition of B imparted an increase in electron density and affected the reducibility of Pt sites. In addition, incorporating B on SiO2 created anchoring sites for Pt ALD. The amount of Pt deposited on B/SiO2 was 2.2 times that on SiO2. Catalytic activity results revealed the addition of B did not change the initial activity of Pt sites significantly, but improved propylene selectivity from 80% to 87% and stability almost threefold. The enhanced selectivity and stability of PtB/SiO2 is most presumably due to favored desorption of propylene and mitigating coke formation under reaction conditions, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Comparison of Geochemical Reactivity of Marcellus and Caney Shale Based on Effluent Analysis

ABSTRACT: In this comparative study, we analyzed the changes in elemental concentrations of hydraulic fracturing fluids after interaction with the Marcellus and Caney Shale formations. The focus was on assessing the inherent risks and environmental implications associated with flowback waters, including their impact on soil, ground, and drinking water quality, and human health safety. The chemical compositions of effluents were determined through Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) and Mass spectrometry (ICP-MS). The Marcellus Shale, showed concentrations of Cd, averaging 0.380 ppm far exceeding safe water thresholds. Significant levels of As, Se, B, and Pb were detected in both shales, raising concerns about soil and water contamination. Analyzing the effluents from representative samples of sections of the Marcellus (S2 and S7) and Caney (R1 and R2) indicates different geochemical responses over 4 weeks of experiments. This comparison underscores the chemical changes and environmental considerations linked to hydraulic fracturing across shale formations, suggesting the value of tailored monitoring and regulatory measures for each type. 1. INTRODUCTION The Caney and Marcellus shales, differing in geology and geochemistry, represent distinct unconventional reservoirs. The Caney shale, is more ductile, with higher produced water volumes, (Smith et al., 2022) contrasts with the brittle Marcellus shale known for lower brine production but significant data availability. This study aims to elucidate the possible environmental health and safety issues that may arise from the hydraulic fracturing processes. The interaction between fracturing fluids and clays presents a significant challenge. The primary base of these fluids is water, which, when introduced to clay, can induce swelling and constrict flow pathways. This phenomenon is attributed to water molecules infiltrating the layers of clay, particularly in 2:1-type clays, leading to an increased distance between layers. To counteract this, clay stabilizers are employed (Awejori et al., 2021). Despite their effectiveness, these stabilizers are considered temporary solutions. Upon completion of the fracturing process, a concomitant amount of contaminated waters (flow back), with varied content is collected at the surface. From these, we can infer the geochemical reactions and the environmental challenges associated with these waters. Flowback waters can be reinjected or used for other purposes such as irrigation. This requires adequate screening and treatment for safe use.

Dje, L. B.↗

Standard Analytical Methods for Pyrolysis Bio-Oils

There has been significant recent interest in the production of renewable fuels and chemicals from biomass and waste feedstocks. Pyrolysis pathways produce a liquid bio-oil product, which must be processed further, or upgraded, to yield fuel or chemical products. Bio-oils are very complex and often unstable samples, and research and development on upgrading processes needs reliable analytical information. In particular, chemical characterization techniques are needed to quantify both functional groups and individual compounds present in bio-oils. Reliable analytics are also needed to enable the bioenergy industry, as industrial facilities often have different analytical needs and capabilities than research facilities. In this presentation, we will discuss the development of a suite of standard analytical methods for pyrolysis bio-oils. Analytical methods to be discussed include: Determination of Carbon, Hydrogen, Nitrogen, and Oxygen in bio-oils; Accelerated Aging of Fast Pyrolysis Bio-oil using Carbonyl Titration; Determination of Water Content in Bio-oils by Volumetric Karl Fischer Titration; Determination of Carbon Functional Groups; Elemental Analysis of Bio-oils by Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) - Na, K, Mg, Ca, S, P, and Fe; Determination of Phenolic Groups in Bio-oils using Revised Folin-Ciocalteu Methods: Single Cuvette and Plate Reader; Corrosivity of Bio-oils: Screening Test using Metal Leaching; Determination of Biogenic Content by 14C Measurement using Liquid Scintillation Counter. These new analytical methods are publicly available as Laboratory Analytical Procedures (https://www.nrel.gov/bioenergy/bio-oil-analysis.html), along with previously developed standard methods: GC-MS, Acid Titration, Carbonyl Titration, and 31P NMR. Additionally, the development of diffusion ordered NMR for characterization of bio-oil molecular weight will be discussed. Collectively, this suite of analytical methods represents the most comprehensive set of standard methods available for pyrolysis bio-oils. These standard methods are commonly used by the bioenergy community, and provide reliable information that enables research, scaleup, and industrial processing of biomass to produce renewable fuels and chemicals.

analytical↗

Wavelength modulation laser-induced fluorescence for plasma characterization

Laser-Induced Fluorescence (LIF) spectroscopy is an essential tool for probing ion and atom velocity distribution functions (VDFs) in complex plasmas. VDFs carry information about the kinetic properties of species that is critical for plasma characterization. Accurate interpretation of these functions is challenging due to factors such as multicomponent distributions, broadening effects, and background emissions. Our research investigates the use of Wavelength Modulation (WM) LIF to enhance the sensitivity of VDF measurements. Unlike standard Amplitude Modulation (AM) methods, WM–LIF measures the derivative of the LIF signal. This approach makes variations in VDF shape more pronounced. VDF measurements with WM–LIF were investigated with both numerical modeling and experimental measurements. The developed model enables the generation of both WM and AM signals, facilitating comparative analysis of fitting outcomes. Experiments were conducted in a weakly collisional argon plasma with magnetized electrons and non-magnetized ions. Measurements of the argon ion VDFs employed a narrow-band tunable diode laser, which scanned the 4p 4 D 7/2 –3d 4 F 9/2 transition centered at 664.553 nm in vacuum. A lock-in amplifier detected the second harmonic WM signal, which was generated by modulating the laser wavelength with an externally controlled piezo-driven mirror of the diode laser. Finally, our findings indicate that the WM–LIF signal is more sensitive to fitting parameters, allowing for better identification of VDF parameters such as the number of distribution components, their temperatures, and velocities. In addition, WM–LIF can serve as an independent method to verify AM measurements and is particularly beneficial in environments with substantial light noise or background emissions, such as those involving thermionic cathodes and reflective surfaces.

47 OTHER INSTRUMENTATION↗

Gold L-shell emission spectroscopy as a temperature diagnostic in laser-driven experiments

Measurements of plasma conditions within gold hohlraums are challenging but provide important information about hohlraum energy transport. To date, there are no reliable passive diagnostic approaches that produce information about the hohlraum plasma conditions. Gold L-shell emission spectroscopy is a promising method to measure the electron temperature in multi-keV gold hohlraum plasmas. In this study, we compare time-resolved measurements of gold L-shell spectra against a more conventional electron temperature-sensitive diagnostic, K-shell emission from zinc, a mid-Z dopant. The Au L-shell and Zn K-shell spectra are taken simultaneously. The analysis of both sets of data exhibits good agreement with a singular rad-hydro model, suggesting a similar evolution in the mean electron temperature of the hohlraum plasma. These findings support the use of L-shell spectroscopy of gold as a method to study gold plasma conditions.

Emission spectroscopy↗

Local measurements of the pedestal magnetic field profile throughout the ELM cycle on DIII-D

We report new high speed localized measurements of the pedestal magnetic field during the edge localized mode (ELM) cycle of a DIII-D High confinement mode (H-mode) discharge indicate a temporally and spatial complex redistribution of the edge current density profile, $j_{edge}$. The measurement technique extracts the magnetic field magnitude, $\textit{B}$, via the spectral separation of Stark-split neutral beam radiation in the pedestal. Single spatial channel measurements from a novel spatial heterodyne spectrometer are validated in discharges with core current profile changes. The technique measures Stark-splitting changes that imply $\textit{B}$ changes as small as 1 mT with high time resolution (50 μs). At normalized poloidal flux $ψ_n$ = 1.0, $\textit{B}$ appears saturated in the inter-ELM period and then rapidly decreases in <200 μs by ~1%, before edge recycling emission begins to increase. Radially inboard of $j_{edge}$, $\textit{B}$ increases at the ELM crash. The behavior is consistent with a rapid collapse of $j_{edge}$ at the ELM crash and subsequent pedestal recovery. In some discharges, at $ψ_n$ < 0.96, changes in $\textit{B}$ are observed throughout the ELM cycle. In others, $\textit{B}$ recovers and is relatively stable until a few ms leading up to the next crash. Measurements of $\textit{B}$ during the H-mode transition show a large increase at $ψ_n$ = 1 with little change at $ψ_n$ = 0.9, consistent with the formation of the edge bootstrap current density peak. The $ψ_n$ = 0.9 spectrum is complicated by predicted changes to the Stark component intensities with density at the L–H transition.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Simultaneous measurements of forward Thomson scattering and rotational Raman scattering in a weakly ionized plasma

This paper demonstrates a simultaneous Thomson scattering and rotational Raman scattering spectroscopy in a weakly ionized plasma in air. Thomson scattering was collected in the forward scattering direction, in order to compress the relative spectra width of Thomson scattering from the plasma. Simultaneous measurements of rotational Raman scattering were obtained in the same direction, which was not affected by the collection angles. The measurements thus yielded electron temperature (T e ) and electron number density (n e ) as well as gas temperature in a weakly ionized atmospheric pressure plasma. The separation of rotational Raman scattering and Thomson scattering occurred when the scattering angle decreased to 20 degrees in the plasma, where the air temperature was found to be 150 ± 25 °C, and electron temperature of the plasma was 0.587 ± 0.087 eV, and electron number density was (1.608 ± 0.416) × 1021 m-3. The technique could be used for various plasma and combustion diagnostics in realistic engineering environments.

He, Zichen (ORCID:0000000183159882)↗

Optical emission spectroscopy and imaging of low-pressure N2 plasmas generated by intense fast-pulsed electron beams

An optical emission spectroscopic (OES) and imaging characterization is conducted on N2 plasmas generated by a 100 keV fast-pulsed electron beam. The electron beams are injected into an N2 gas filled volume with a current of 4.5 kA (300 A/cm2) and a 100 ns pulse width. The characterization is conducted at the pressures, 1 Torr and 0.1 Torr, corresponding to two distinct regimes that exhibit significantly different plasma dynamics. Beam impact ionization is shown to be a primary mechanism for producing low temperature plasmas at 1 Torr during beam output. After beam termination, ionization by an inductive electric field becomes the primary mechanism for plasma formation later in time for both pressures. OES and plasma imaging are used in this work as a diagnostic tool to track the distribution of electronic, vibrational, and rotational state transitions and ionized species. This is achieved with the use of a multi-resolution suite of spectrometers capable of acquiring time-resolved spectra. Vibrational and rotational bands of the N2 second positive system (C3Πu→B3Πg) and the N2+ first negative system (B2Σu+→X2Σg+) are identified in both regimes as well as N+ states exclusively in the lower pressure regime. Vibrational and rotational spectra are shown to track the evolution of the time-varying plasma current. Plasma imaging also reveals spatially nonuniform plasma emission at 0.1 Torr. A few hundred shots are recorded to fully characterize the emissions, and results are shown to be highly reproducible (≤±1% with 2σ confidence).

Kaiser, E. R. (ORCID:0000000336493938)↗

Extended X-ray absorption spectroscopy using an ultrashort pulse laboratory-scale laser-plasma accelerator

Laser-driven compact particle accelerators can provide ultrashort pulses of broadband X-rays, well suited for undertaking X-ray absorption spectroscopy measurements on a femtosecond timescale. Here the Extended X-ray Absorption Fine Structure (EXAFS) features of the K-edge of a copper sample have been observed over a 250 eV window in a single shot using a laser wakefield accelerator, providing information on both the electronic and ionic structure simultaneously. This capability will allow the investigation of ultrafast processes, and in particular, probing high-energy-density matter and physics far-from-equilibrium where the sample refresh rate is slow and shot number is limited. For example, states that replicate the tremendous pressures and temperatures of planetary bodies or the conditions inside nuclear fusion reactions. Using high-power lasers to pump these samples also has the advantage of being inherently synchronised to the laser-driven X-ray probe. A perspective on the additional strengths of a laboratory-based ultrafast X-ray absorption source is presented.

43 PARTICLE ACCELERATORS↗

Time-resolved absorption spectroscopic characterization of ultrafast laser-produced plasmas under varying background pressures

Time-resolved tunable laser absorption spectroscopy is used to characterize the physical properties of ultrafast laser-produced plasmas. The plasmas were produced from an Inconel target, with = 0.4 wt. % Al, using ~ 35 fs, ~800 nm laser pulses at varying Ar background pressures from 1-100 Torr. The absorption spectrum of atomic Al is measured with high spectral and temporal resolution when the probe laser is stepped across the selected Al transition at 394.4 nm. Spectral fitting is used to infer linewidths, kinetic temperature, Al column density, and pressure broadening coefficient. The late time physical properties of plasmas are compared for various pressure levels. Our studies highlight that a significant lower state population exists even at early times of ultrafast laser-produced plasma evolution and lower state population persistence decreases with increasing ambient pressure. We also show that the fundamental optical properties, such as pressure-broadening, can be measured using ultrafast laser-produced plasmas combined with laser absorption spectroscopy.

laser absorption spectroscopy, laser produced plas↗

Impact of strong magnetization in cylindrical plasma implosions with applied B-field measured via x-ray emission spectroscopy

Magnetization is a key strategy for enhancing inertial fusion performance, though accurate characterization of magnetized dense plasmas is needed for a better comprehension of the underlying physics. Measured spectra from imploding Ar-doped D 2 -filled cylinders at the OMEGA laser show distinctive features with and without an imposed magnetic field. A multizone spectroscopic diagnosis leads to quantitative estimates of the plasma conditions, namely revealing a 50% core temperature rise at half mass density when a 30-T seed field is applied. Concurrently, experimental spectra align well with predictions from extended-magnetohydrodynamics simulations, providing strong evidence that the attained core conditions at peak compression are consistent with the impact of a 10-kT compressed field. These results pave the way for the validation of magnetized transport models in dense plasmas and for future magnetized laser implosion experiments at a larger scale. Published by the American Physical Society 2024

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Collisionless Larmor coupling and blob formation in a laser-plasma expanding into a magnetized ambient plasma

Collisionless Larmor coupling is a fundamental process in space and astrophysical plasmas that enables momentum transfer between an expanding plasma and a magnetized ambient medium. Here, in this paper, we report on the laboratory experimental study of Larmor coupling leading to the formation of a plasma blob associated with a laser-driven, super-Alfvénic plasma flow on the Large Plasma Device at the University of California, Los Angeles. The high-repetition rate enables systematic spatial and temporal scans of the plasma evolution using Doppler spectroscopy, as well as measurements of the magnetic field, electrostatic field, and self-emission of both debris and ambient ions using filtered imaging. We observe the self-focusing of the laser-produced plasma and the formation of a secondary diamagnetic cavity associated with a blob composed of background ions. Doppler spectroscopy reveals the transverse velocity distribution of the background ions, providing direct evidence of ion energization via Larmor coupling. The systematic spatial and temporal scans enabled by the high-repetition-rate experiment allow for a detailed characterization of the ion dynamics. These experimental observations are supported by numerical simulations that provide more insight into the kinetic-scale physics associated with blob formation as well as the role of the ambient plasma density.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Observation of shock-front separation in multi-ion-species collisional plasma shocks

We observe shock-front separation and species-dependent shock widths in multi-ion-species collisional plasma shocks, which are produced by obliquely merging plasma jets of a He/Ar mixture (97% He and 3% Ar by initial number density) on the plasma liner experiment. Visible plasma emission near the He-I 587.6-nm and Ar-II 476.5–514.5-nm lines is simultaneously recorded by splitting a single visible image of the shock into two different fast-framing cameras with different narrow bandpass filters (589 ± 5 nm for observing the He-I line and 500 ± 25 nm for the Ar-II lines). For conditions in these experiments (pre-shock ion and electron densities ≈5×10 14 cm –3 , ion and electron temperatures of ≈2.2 eV, and relative plasma-merging speed of 22 km/s), the observationally inferred magnitude of He/Ar shock-front separation and the shock widths themselves are <1 cm, which correspond to ~50 post-shock thermal ion–ion mean free paths. These experimental length scales are in reasonable qualitative and quantitative agreement with results from 1D multi-fluid simulations using the CHICAGO code. However, we note there are differences between the experimentally inferred and simulation-predicted ionization states and line emission intensities, particularly in the post-shock region. Overall, the experimental and simulation results are consistent with theoretical predictions that the lighter He ions diffuse farther ahead within the overall shock front than the heavier Ar ions.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

The effect of ICRH and NBI on tungsten transport in neon edge radiation cooled discharges in TEXTOR

Tungsten is planned to be the plasma-facing material for the main chamber and divertor in future devices like ITER, SPARC, and DTT. To address risks associated with tungsten, R&D is being carried out on various toroidal confinement devices. One particular research question is related to the optimum heating mix for ITER. To investigate the influence of the heating scheme on the release and transport of tungsten, a comparison of neutral beam injection (NBI) and ion cyclotron resonance frequency (ICRF) heating was carried out in TEXTOR tungsten test limiter experiments. The experiments were performed under standard L-mode conditions and in radiative improved-mode operation with neon seeding and boronized walls covering the graphite plasma-facing components. The plasma was heated with hydrogen or deuterium NBI alone or with deuterium NBI in combination with H-minority, ion cyclotron resonance heating. A movable solid tungsten limiter was inserted through a limiter lock system into the edge plasma. The impurity release from this limiter was evaluated from visible spectroscopy. The tungsten concentrations in the plasma core were determined by extreme ultraviolet spectroscopy and bolometry. With deuterium NBI alone, strong central radiation and accumulation of W was observed. This can, however, be avoided by adding ICRF heating.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Soft X‐Ray Absorption Spectroscopy With a Flat Liquid Jet in Vacuum Using a Table‐Top Laser‐Induced Plasma Source

ABSTRACT In this work, we demonstrate the integration of a flat liquid jet sample delivery system into a compact soft x‐ray absorption spectrometer using a table‐top laser‐induced plasma source. A high‐speed flat liquid sheet is formed by the collision of two cylindrical jets. This micrometer‐thin lamella can ideally be utilized for transmission‐mode soft x‐ray absorption spectroscopy using krypton plasma emission. Detailed analysis of the jet's thickness profile is achieved applying Lambert–Beer's law. Measurements on water, focusing on the oxygen K‐edge, reveal a lamella thickness profile ranging from 500 nm to 1 μm over a length of 3.8 mm. Additionally, we have investigated aqueous solutions of iron salts, capturing near edge x‐ray absorption fine structure spectra over a broad spectral range from the nitrogen K‐edge to the iron L‐edge. Focused analysis on iron species in aqueous solutions enabled us to distinguish quantitatively between the oxidation states of Fe 2+ and Fe 3+ at the iron L‐edge. Our results are compared with measurements obtained under similar conditions at a synchrotron.

Holburg, Jonathan [Department Optics/Short Wavelen↗

Small-scale production of bespoke accelerated aging plutonium alloy

Here, this study demonstrates the 100 g scale manufacture of a plutonium alloy that ages at an accelerated rate. The resulting alloy ages six times faster than typical weapons-grade plutonium due to the addition of 238 Pu. As a major innovation, the process involved using a partial direct oxide reduction technique. This method was achieved by developing a new, complex geometry stirrer using additive manufacturing to reduce the 238Pu oxide and efficiently incorporate it into weapons-grade plutonium metal. The material was then purified by molten salt extraction and electrorefining before being alloyed with gallium. The alloy was then cold-rolled and annealed in a homogenization heat treatment. The resulting disk was characterized by metallography and differential scanning calorimetry, and the impurity content was determined using analytical chemistry techniques. The results show that a homogeneous delta phase plutonium alloy was achieved with expected microstructure and minimal impurities. This study was also successful in changing the plutonium isotopic composition by incorporating additional 238 Pu to accelerate the effects of radiation damage. This enables researchers to study long-term aging phenomena in a reduced time frame, thus avoiding the need for large-scale material production and circumventing the limitations of using naturally aged, archived plutonium.

Aging theory↗