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At least 991 records · Page 55

Growth of AlGaAs, AlInP, and AlGaInP by Hydride Vapor Phase Epitaxy

In this work, we demonstrate hydride vapor phase epitaxy (HVPE) of Al x Ga 1-x As, Al x In 1-x P, and Al x Ga y In 1-x-y P using an AlCl 3 precursor. We study the growth of the Al x Ga 1-x As alloy system to elucidate the effects of deposition temperature, V/III ratio, and group V precursor species on Al solid incorporation via AlCl 3 . Crucially, the presence of group V hydride at the growth front kinetically promotes the solid incorporation of Al. We use these insights to demonstrate controlled deposition of Al x Ga 1-x As, and for the first time by HVPE, Al x In 1-x P and Al x Ga y In 1-x-y P. Finally, these results create exciting implications for HVPE-grown high-efficiency III-V solar cells and devices with reduced cost.

14 SOLAR ENERGY↗

Project 18-15263 X-ray Studies of Interfacial Molecular Complexes in ALSEP Back-Extraction (Research Performance Final Report)

The objective of the project was to use synchrotron X-rays to measure the molecular-scale organization of extractants, complexants, buffers, and metal ions at the organic-aqueous (liquid-liquid) interface during solvent back-extraction under conditions relevant to ALSEP (Actinide-Lanthanide Separation Process). The capability of X-ray fluorescence near total reflection (XFNTR) was extended to explore the distribution of Eu(III) between the liquid-liquid interface and bulk organic and aqueous phases which contained extractants HDEHP (bis(2-ethylhexyl) phosphoric acid) and HEHEHP (2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester), the complexant DTPA (diethylene triamine pentaacetic acid), and citric and nitric acids. Although an Am-compatible sample cell was developed, extending x-ray measurements of flat liquid-liquid interfaces to the actinide Am(III) did not prove to be possible within constraints imposed by the Advanced Photon Source. However, preliminary measurements with a drop cell may eventually provide a path forward to investigate Am(III) at a liquid interface. It was also demonstrated that competitive binding that occurs during back-extraction of lanthanide ions to either a phosphoric acid extractant (DHDP, di-hexadecyl phosphate) at the liquid interface or to complexant DTPA in the bulk aqueous phase could be reversibly tuned by X-ray exposure. Separately, X-ray measurements from the liquid-vapor interface explored the role of the aqueous solubility of HDEHP and HEHEHP and their interactions with a range of lanthanides and transition metal ions. Finally, the capability of X-ray absorption spectroscopy (EXAFS) was extended to probe metal ion coordination in lanthanide ion-extractant complexes at the liquid-vapor interface. Complementary to the specific interfacial systems studied during this project, the development of x-ray techniques expands our ability to understand ion ordering at liquid interfaces.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Low-Cost III-V Photovoltaic Materials by Chloride Vapor Transport Deposition Using Safe Solid Precursors

Si-based photovoltaic devices dominate the market. As photovoltaic (PV) manufacturing costs have plummeted, technologies which increase efficiency have become critical. Si cell efficiencies are nearing theoretical limits and Si-based PV modules are unlikely to reach the 25-30% efficiency range. The use of III-V semiconductors is an obvious technical solution to improve efficiency, especially if they can be integrated directly with existing Si technology as tandems. High coefficients of light absorption along with tunable bandgaps and lattice constants have resulted in record conversion efficiencies for both one-sun and concentrator PV applications. GaAs, for example, has been used to manufacture single-junction photovoltaics with world-record efficiencies of 28.8% at one sun.2 However, costs for III-Vs must be dramatically reduced to produce cost-effective, high-efficiency PV solutions. III-V costs are controlled by two factors: semiconductor growth and the substrate. III-V growth is dominated today by metal-organic vapor phase epitaxy (MOVPE) with a lesser role played by molecular beam epitaxy (MBE). MOVPE costs are high due to the expense and low utilization (~30%) of precursors, modest growth rates (~100 nm min -1 ), equipment complexity, and safety infrastructure needed to handle toxic, pyrophoric gases.3 MBE costs are high due to slow growth rates and limitations of scalability. Details comparing plausible low-cost III-V growth methods are available in a review article published as a result of this project. The primary goal of this project was to demonstrate that close-spaced vapor transport (CSVT) using chloride (from HCl) as a transport agent can be used for the rapid growth of device-ready III-V layers from safe, solid-source precursors. In pursuit of this goal, we designed, built, and installed a new Cl-CSVT reactor based on insights from our previous H 2 O-CSVT growth system and in collaboration with equipment professionals at Malachite Technologies. This system was successfully used to grow epitaxial GaAs with controlled n-type doping, having mobilities similar to MOVPE. Detailed technical information and results can also be found in the primary publication resulting from this project. This work sets the stage for tackling the development of high-performance III-V single junctions and tandem devices directly on Si substrates, which was beyond the capabilities of our H2O-CSVT system. The design of the reactor’s source and substrate transfer system should allow for direct deposition of device structures. The collective innovations of our Cl-CSVT system might ultimately serve as an enabling process for commercialization of the technology through a collaboration with appropriate industrial partners.

14 SOLAR ENERGY↗

Material growth and characterization for solid state devices

During the period of this research grant, the process of liquid phase electroepitaxy (LPEE) was used to grow ternary and quaternary alloy III-V semiconductor thin films. Selective area growth of InGaAs was performed on InP substrates using a patterned sputtered quartz or spin-on glass layer. The etch back and growth characteristics with respect to substrate orientation were investigated. The etch back behavior is somewhat different from wet chemical etching with respect to the sidewall profiles which are observed. LPEE was also employed to grow epitaxial layers of InGaAsP alloys on InP substrates. The behavior of Mn as an acceptor dopant was investigated with low temperature Hall coefficient and photoluminescence measurements. A metal-organic vapor phase epitaxy system was partially complete within the grant period. This atmospheric pressure system will be used to deposit III-V compound and alloy semiconductor layers in future research efforts.

Collis, Ward J.↗

Magnetic properties of nanocrystalline ε-Fe{sub 3}N and Co{sub 4}N phases synthesized by newer precursor route

Graphical abstract: Nanocrystalline ε-Fe{sub 3}N and Co{sub 4}N nitride phases are synthesized first time by newer chemical routes. The ε-Fe{sub 3}N phase crystallizes in hexagonal structure with unit cell parameters, a = 4.76 Å and c = 4.41 Å. The Co{sub 4}N phase crystallizes in face centred cubic (fcc) structure with unit cell parameters, a = 3.55 Å. The estimated crystallite size for ε-Fe{sub 3}N and Co{sub 4}N phases are 29 nm and 22 nm, respectively. The values of saturation magnetization for ε-Fe{sub 3}N and Co{sub 4}N phases are found to be 28.1 emu/g and 123.6 emu/g respectively. The reduction of magnetic moments in ultrafine materials compared to bulk materials has been explained by fine particle size and surface effects. We have synthesized the high moment ε-Fe{sub 3}N and Co{sub 4}N nitride with reduced coercivity which may find applications as soft magnetic materials. - Highlights: • Nanocrystalline ε-Fe{sub 3}N and Co{sub 4}N nitride phases are synthesized. • The ε-Fe{sub 3}N and Co{sub 4}N crystallizes in hexagonal and fcc structure respectively. • The observed magnetic parameters indicate soft magnetic properties. • The magnetic properties have been explained on the basis of fine particle magnetism. - Abstract: Nanocrystalline ε-Fe{sub 3}N and Co{sub 4}N nitride phases are synthesized first time by using tris(1,2-diaminoethane)iron(II) chloride and tris(1,2-diaminoethane)cobalt(III) chloride precursors, respectively. To prepare ε-Fe{sub 3}N and Co{sub 4}N nitride phases, the synthesized precursors were mixed with urea in 1:12 ratio and heat treated at various temperatures in the range of 450–900 °C under the ultrapure nitrogen gas atmosphere. The precursors are confirmed by FT-IR study. The ε-Fe{sub 3}N phase crystallizes in hexagonal structure with unit cell parameters, a = 4.76 Å and c = 4.41 Å. The Co{sub 4}N phase crystallizes in face centred cubic (fcc) structure with unit cell parameters, a = 3.55 Å. The estimated crystallite size for ε-Fe{sub 3}N and Co{sub 4}N phases are 29 nm and 22 nm, respectively. The scanning electron microscopy (SEM) studies confirm the nanocrystalline nature of the materials. The values of saturation magnetization for ε-Fe{sub 3}N and Co{sub 4}N phases are found to be 28.1 emu/g and 123.6 emu/g, respectively. The reduction of magnetic moments in ultrafine materials compared to bulk materials have been explained by spin pairing effect, lattice expansion, superparamagnetic behaviour and canted spin structures at the surface of the particles.

36 MATERIALS SCIENCE↗

Ab Initio Phase Diagram of Tungsten

The phase diagram of tungsten (W) to a pressure (P) of 2500 GPa is investigated using a comprehensive ab initio approach that includes (i) the calculation of the zero temperature (T) free energies (enthalpies) of different solid structures, (ii) the quantum molecular dynamics simulation of the melting curves of different solid structures, (iii) the derivation of the analytic form for the solid-solid phase transition boundary, and (iv) the simulations of the solidification of liquid W into the final solid states on both sides of the solid-solid phase transition boundary, in order to confirm the corresponding analytic form. There are two solid structures confirmed to be present on the phase diagram of W, the ambient body-centered cubic (bcc) and the high-pressure double hexagonal close-packed (dhcp). At T = 0, the bcc-dhcp transition occurs at 1060 GPa, and the transition boundary has a positive slope dT/dP : the bcc-dhcp-liquid triple point is at (P, T) = (1675 GPa, 23680 K).

36 MATERIALS SCIENCE↗

Computational and Experimental Investigation of Thermal-Mechanical- Chemical Mechanisms of High-burnup Spent Nuclear Fuel (SNF) Processes at Elevated Temperatures and Degradation Behavior in Geologic Repositories

The overarching goal of the combined computational and experimental R&D activities proposed in this project is to enhance understanding of the mechanisms and thermal-mechanical-chemical (TMC) parameters controlling the instant release fraction (IRF) and matrix dissolution of high-burnup (HB; burnup) spent nuclear fuels (SNFs) and the subsequent formation, stability, and phase transformations of SNF alteration products under long-term storage and geological disposal conditions. Uranium dioxide may undergo oxidative corrosion/alteration, and the IRF may be increased for HB SNF, both of which may affect environmental systems associated with SNF long-term storage and disposal. The oxidative matrix dissolution may form various complex uranyl-based phases, including a rich variety of oxides, silicates, carbonates and other secondary minerals in varied geological environments (e.g., studtite, metastudtite, amorphous uranyl peroxide, uranium trioxide, triuranium octoxide, schoepite, dehydrated schoepite, metaschoepite, becquerelite, soddyite, rutherfordine,...). These uranyl phases generally have higher mobility UO 2 +2 species than less soluble U 4+ phases. However, limited information on the thermodynamic properties and formation kinetics of these uranyl-bearing phases is available to predict explicitly paragenesis under the conditions relevant to long-term storage or disposal. The proposed project draws on complementary expertise and research backgrounds from the team members: (i) to apply a combined ab initio modeling (UNLV/UTEP and SNL) and experimental (UNLV) strategy investigating the high-temperature TMC mechanisms of alteration of SNF under α-radiolysis conditions; (ii) to investigate the mechanistic of phase transformations in UNF degradation products under various conditions expected in long-term storage systems (e.g. (UO 2 )O 2 (H 2 O) 4 → (UO 2 )O 2 (H 2 O) 2 → U 2 O 7 → UO 3 → U 3 O 8 ); (iii) to determine high-accuracy TMC parameters for complex uranyl-based phases formed in storage or geological disposal environments (e.g. UO 3 (H 2 O) 2 , Ca[(UO 2 ) 6 O 4 (OH) 8 ] 8 H 2 O, (UO 2 ) 2 (SiO 4 ) 3 2H 2 O,…). The unforeseen COVID-19 pandemic led to the laboratory/campus closure since March 2020, that resulted in a significant delay in reaching milestones in a satisfactory manner, due to (i) the statewide recommendation from stop-working to later limited work in the lab and work-from-home (WFH), (ii) no in-person interactions, and (iii) a hiring freeze at UNLV. Therefore, a no cost extension (10/01/2021- 9/30/2022) was requested to help make up the time we lost during the global pandemic in 2020-2021, leading to paradigm shifts in the focus of the project in the following three main tasks: Task 1 (Computational), Task 2 (Experimental), and Task 3 (Final report, due on 12/29/2022).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Interface atomic structures in a cadmium arsenide/III–V semiconductor heterostructure

The interface atomic structure between an epitaxial thin film of the prototype topological semimetal cadmium arsenide (Cd 3 As 2 ) and a III–V semiconductor layer is investigated using high-angle annular dark-field imaging in an aberration-corrected scanning transmission electron microscope. We find that the interface unit cell adopts a defined stoichiometry that is CdSb-like, which is achieved through the insertion of periodically arranged Cd vacancies in the terminating Cd-plane of Cd 3 As 2 . This interface stoichiometry is consistent with the Sb-termination of the III–V layer and the fact that CdSb is the thermodynamically stable phase in the Cd–Sb binary system. We find at least two distinct alignments of the film with respect to the buffer layer, which are characterized by a $\frac{1}{4}$ <100> Cd 3 As 2 shift parallel to the interface. We show that steps of half unit cell height in the III–V layer can produce these distinct interface structures.

74 ATOMIC AND MOLECULAR PHYSICS↗

Soft-donor dipicolinamide derivatives for selective actinide( iii )/lanthanide( iii ) separation: the role of S- vs. O-donor sites

Selectivity for An(III) vs. Ln(III) binding and extraction with dipicolinamide analogs containing the C=O vs. C=S groups was investigated in solution and the gas-phase, and by DFT calculations. The results reflect higher selectivity for complex formation and extraction for Am(III) vs. Eu(III) for the softer dithioamide vs. the diamide ligand, while in CH 3 CN the diamide binds more strongly than the thioamide to several Ln(III), forming 1:1 complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Predicting zeolites’ stability during the corrosion of nuclear waste immobilization glasses: Comparison with glass corrosion experiments

During the long-term corrosion of nuclear waste glasses under nuclear waste disposal conditions, the precipitation of zeolitic phases has been linked to a delayed acceleration in glass corrosion (known as “Stage III”). Hence, predicting the thermodynamic propensity for zeolites to form upon the dissolution of nuclear waste glasses is key to ensure their long-term performance. Here, we compile a unified, internally-consistent thermodynamic database “clay20” to estimate the stability of clay and feldspar phases relevant to nuclear waste immobilization glasses, including beidellite(Mg, Ca, Na, K), kaolinite, montmorillonite(Mg, Ca, Na, K), nontronite(Mg, Ca, Na, K), saponite(Ca, Na, K), and albite. Based on this, we report a geochemical modeling method allowing us to predict the stability of secondary phases (including zeolites, calcium–silicate–hydrate gels, and clays) upon the dissolution of nuclear waste immobilization glasses. We show that this approach offers a realistic description of the stability of the secondary phases forming during the dissolution of two archetypical model nuclear glasses (namely, the International Simple Glass, ISG, and WVUTh-203) under conditions relevant to nuclear waste disposal (T = 90°C, p = 1 bar) as a function of pH. We find that the formation of silica and clay secondary phases is thermodynamically favored at low pH (pH < 10), whereas, in contrast, zeolite (analcime) and calcium–silicate–hydrate phases are favored at high pH (pH > 10.5). This suggests that thermodynamics (i.e., not solely kinetics) plays a key role in determining the range of solution pH wherein stage III corrosion may occur, i.e., when zeolite formation is favored.

Zhen-Wu, Bi Yun↗

Organic and Aqueous Redox Speciation of Cu(III) Periodate Oxidized Transuranium Actinides

A hexavalent group actinide separation process could streamline used nuclear fuel recycle and waste management. The limiting factor to such a process compatible with current fuel dissolution practices is obtaining and maintaining hexavalent Am, in molar nitric acid due to the high reduction potential of the Am(VI)/Am(III) couple (1.68 V vs SCE). Two strong oxidants, sodium bismuthate and Cu(III) periodate, have demonstrated quantitative oxidation of Am under molar acid conditions and better than 50% recovery by diamyl amylphosphonate (DAAP) is possible under these same conditions. This work considers the use of Cu(III) periodate to oxidize Np(V) to Np(VI) and Pu(IV) to Pu(VI) and recover these elements by extraction with DAAP. A metal:oxidant ratio of 1:1.2 and 1:3 was necessary to quantitatively oxidize Np(V) and Pu(IV), respectively, to the hexavalent state. Extraction of hexavalent Np, Pu, and Am by 1 M DAAP in n-dodecane was measured using UV-Vis [Pu(VI), Am (VI)] and NIR [Np(VI)]. Distribution values of Am(VI) were found to match previous tracer level studies. The organic phase spectra of Np, Pu, and Am are presented and molar absorptivities are calculated for characteristic peaks. Hexavalent Pu was found to be stable in the organic phase while Np(VI) showed some reduction to Np(V) and Am was present as Am(III), Am(V), and Am(VI) species in aqueous and organic phases during the extraction experiments. These results demonstrate, for the first time, the ability to recover macroscopic amounts of americium that would be present during fuel reprocessing and are the first characterization of Am organic phase oxidation state speciation relevant to a hexavalent group actinide separation process under acidic conditions.

americium↗

A unified N-body and statistical treatment of stellar dynamics. III - Early postcollapse evolution of globular clusters

The period immediately following the core collapse phase in the evolution of a globular cluster is studied using a hybrid N-body/Fokker-Planck stellar dynamical code. Several core oscillations of the type predicted in earlier work are seen. The oscillations are driven by the formation, hardening, and ejection of binaries by three-body processes, and appear to decay on a timescale of about 10 to the 7th yr, for the choice of 'typical' cluster parameters made here. There is no evidence that they are gravothermal in nature. The mechanisms responsible for the decay are discussed in some detail. The distribution of hard binaries produced by the oscillations is compared with theoretical expectations and the longer term evolution of the system is considered.

Mcmillan, S. L. W.↗

Electrospray production and collisional dissociation of lanthanide/methylsulfonyl anion complexes: Sulfur dioxide anion as a ligand

For this study, gas-phase lanthanide-SO 2 complexes, Ln(CH 3 SO 2 ) 3 (SO 2 ) - , were produced by collision induced dissociation (CID) of Ln(CH 3 SO 2 ) 4 - precursors prepared by electrospray ionization. For all lanthanides except Eu, CID of Ln(CH 3 SO 2 ) 4 - resulted in CH 3 loss to form Ln(CH 3 SO 2 ) 3 (SO 2 ) - , which spontaneously react with O 2 to form Ln(CH 3 SO 2 ) 3 (O 2 ) - . CID of Eu(CH 3 SO 2 ) 4 - produced only Eu(CH 3 SO 2 ) 3 - , with reduction from Eu(III) to Eu(II). For Ln = Yb and Sm, the Ln(CH 3 SO 2 ) 4 - underwent neutral ligand loss to form Ln(CH 3 SO 2 ) 3 - , which reacted with O 2 to yield Ln(CH 3 SO 2 ) 3 (O 2 ) - , recovering the Ln(III) oxidation state. The CID results show parallels to condensed-phase Ln 3+ /Ln 2+ redox chemistry. Density functional theory (DFT) calculations on Ln(CH 3 SO 2 ) 3 (SO 2 ) - for Ln = La, Yb and Lu reveal that SO 2 acts as a bidentate oxygen bound ligand for doublet ground-state La(CH 3 SO 2 ) 3 (SO 2 ) - and Lu(CH 3 SO 2 ) 3 (SO 2 ) - , while the ground state for Yb(CH 3 SO 2 ) 3 (SO 2 ) - is an open-shell singlet with a monodentate SO 2 ligand. Loss of CH 3 is computed to be much more favorable than neutral ligand loss for La(CH 3 SO 2 ) 4 - and Lu(CH 3 SO 2 ) 4 - , whereas both channels are comparable in energy for Yb(CH 3 SO 2 ) 4 - , in accord with the experiments. DFT results for fragmentation of Cu(CH 3 SO 2 ) 2 - reveal that formation of the organometallic complex, Cu(CH 3 SO 2 )(CH 3 ) - , is energetically most favorable, in agreement with contrasting fragmentation pathways of copper and lanthanide complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Launch Complex 34, SWMU CC054 2023 DNAPL Source Zone Operations, Maintenance, and Monitoring, Site-Wide Long-Term Monitoring, and Hot Spot 6 Air Sparge System Annual Performance Monitoring and Phase Two Expansion Construction Completion Report Cape Canaveral Space Force Station, Florida

This Annual Performance Monitoring Report (PMR) for the Dense Non-Aqueous Phase Liquid (DNAPL) Source Zone (DSZ), Site-Wide Long-Term Monitoring (LTM), and Hot Spot 6 (HS 6) Air Sparge (AS) System presents the results of Year 14 operations and performance monitoring of the hydraulic containment (HC) Interim Measure (IM), details associated with construction and implementation of the HS 6 AS system expansion (Phase Two), and the results of operations and performance sampling of the HS 6 AS IM at Launch Complex 34 (LC34), located at Cape Canaveral Space Force Station (CCSFS), Florida. The timeframe for activities documented in this PMR extends from April 1, 2023 to March 31, 2024. LC34 has been designated Solid Waste Management Unit CC054 under the Kennedy Space Center (KSC) Resource Conservation and Recovery Act Corrective Action Program. The objective of the HC IM at LC34 is to contain the shallow and deep DSZ and surrounding dissolved-phase trichloroethene (TCE) high concentration plume via operation of a hydraulic containment system (HCS). The pre-IM design 300 micrograms per liter (μg/L) TCE groundwater contour was used to establish the deep zone capture area for deep recovery wells, and the shallow zone capture area was defined by the DSZ. The system began operating in 2010, and in 2015, the system was expanded to provide HC for areas within the 300 μg/L TCE groundwater isocontours of HS 3 and 4. In 2018 and 2019, an investigation was conducted to recharacterize the DSZ, which included investigating TCE mass in Layer 7. This data was subsequently used to optimize the pumping rates of the HCS and install additional recovery wells in Layer 7 to more adequately capture residual contaminant mass. The operational period for Year 14 of the HCS was from April 1, 2023 to March 31, 2024. Operational runtime for the system was 94 percent during Year 14, with downtime events attributed to planned maintenance, system repairs, and power outages. As of March 31, 2024, a total of 344,849,634 cumulative gallons of groundwater containing 94,656 pounds of chlorinated volatile organic compounds (CVOCs) have been removed by the HCS. During the reporting period covered under this report, the HCS recovered 31,176,393 gallons and approximately 6,319 pounds of CVOC mass. Total combined influent concentrations of TCE have decreased since startup from approximately 280,000 µg/L (January 2010) to 25,000 µg/L (March 2024). During the reporting period, all effluent concentrations from the HCS (aqueous and vapor) were below regulatory reporting limits, indicating the system continues to operate as intended. Performance monitoring was conducted in January 2024 within the DSZ to evaluate TCE contamination. Groundwater samples were collected via DPT at nine locations, consistent with previous events between 2017 and 2022. Full vertical profile sampling was completed at each DPT from 8 to 98 feet below land surface (bls), at 5-foot intervals. The DPT performance monitoring results are summarized in this PMR. The results revealed TCE remains at concentrations greater than 11,000 µg/L in the DSZ (1-percent solubility, indicative of DNAPL) at eight of the nine DPT locations and at depths ranging from 28 to 98 feet bls. An overall decreasing trend of TCE concentrations was observed in DPT samples during this reporting period, which is a reduction from the previous event (December 2022) and the peak event in December 2021, where TCE percentages appeared to increase in all depth zones because several recovery wells were turned off during the AS pilot study in the DSZ. The maximum TCE concentration in January 2024 was 1,600,000 µg/L in the 53 feet bls depth interval at DPT594 (previous maximum result in 2022 was 1,800,000 µg/L in the 48 feet bls depth interval at DPT599). This maximum concentration in the 53 feet bls depth interval is in the deep capture zone. During the January 2024 DPT event, the largest portion of TCE mass was observed in the 48 feet bls interval above/within Layer 4. This trend remains consistent with previous years and appears to indicate continued mass discharge from Layer 4 (fine-grained unit). In addition to DPT sampling, annual groundwater samples were collected from 11 deep monitoring wells in the DSZ area (Layers 7 and 8) in December 2023 to verify vertical and horizontal delineation. Three of the wells were also sampled biweekly to evaluate operations of recovery well RW21D (screened 86 to 106 feet bls), which was installed in January 2023. Of the Layer 7/8 monitoring sampled only annually, results were non-detect or less than groundwater cleanup target levels GCTLs in December 2023, with the exception of one well, IW45D2, which had a cis-1,2-dichloroethene (cDCE), detection greater than the GCTL. Of the three wells sampled biweekly during the operational period, the well located closest to Layer 7 recovery well RW21D (IW44D2, screened 105 to 115 feet bls) had concentrations of TCE, cDCE and vinyl chloride (VC) greater than GCTLs throughout the operational period, but displayed a decreasing trend since the peak concentrations in September 2023. The maximum TCE concentration during this operational period was 190,000 µg/L at IW44D2 in September 2023, but reduced to 700 µg/L in March 2024, indicating the HCS is still effectively removing mass from the source area. Expansion of the HCS and addition of new recovery wells is ongoing and will continue to be evaluated as the groundwater recovery scheme is optimized. Details of the expansion and optimization will be provided in a future PMR. The HS 6 AS IM was initiated in 2018 with 160 AS wells and expanded in 2019 with another 140 AS wells. An additional expansion of the HS 6 AS IM was completed during the reporting period covered under this report and details of the construction implementation and startup of the expansion are detailed in Section III of this report. The new expansion, referred to as Phase Two, was implemented between August 17, 2022 and August 28, 2023, and included the installation of 190 air sparge wells to treat an additional 11.2 acres. The original configuration (referred to as Phase One) operated until Phase Two came online, then all but 52 AS wells were turned off so the components could be moved and utilized in the Phase Two area. The 52 AS wells that remain on are in a barrier configuration preventing contaminated groundwater from impacting the treated area. The HS 6 AS system (both Phase One and Two) operated normally during the reporting period covered under this report. Semi-annual performance monitoring of the Phase One configuration was conducted in April and November 2023, consistent with previous years. For the Phase Two configuration, 21 new monitoring wells were installed and sampled quarterly, with a baseline event in July 2023, and quarterly events in November 2023 and February 2024 summarized in this report. Semi-annual monitoring results collected in April and October 2023 show concentrations of contaminants of concern (cDCE, trans-1,2-dichloroethene, and VC) have decreased to less than GCTLs in nearly all wells and not impacting the surface water drainage canal, indicating the HS 6 IM continues to meet objectives. The baseline and quarterly sampling for the Phase Two configuration indicate generally decreasing concentrations in wells within and around the perimeter of the treatment area. At least two more quarters of monitoring will be conducted and once those results are evaluated a reduced the sampling frequency may be considered. Overall, the tasks associated with Year 14 operation of the HC IM and operation of the HS 6 AS IM were performed in accordance with recommendations included in the previous 2022 LC34 (Year 13) PMR. Evaluation of results from the HC IM and HS 6 IM show that these systems are operating as designed and meeting performance objectives.

groundwater remediation↗

Phase 1/2 Trials of Temozolomide, Motexafin Gadolinium, and 60-Gy Fractionated Radiation for Newly Diagnosed Supratentorial Glioblastoma Multiforme: Final Results of RTOG 0513

Purpose: The purpose of phase 1 was to determine the maximum tolerated dose (MTD) of motexafin gadolinium (MGd) given concurrently with temozolomide (TMZ) and radiation therapy (RT) in patients with newly diagnosed supratentorial glioblastoma multiforme (GBM). Phase 2 determined whether this combination improved overall survival (OS) and progression-free survival (PFS) in GBM recursive partitioning analysis class III to V patients compared to therapies for recently published historical controls. Methods and Materials: Dose escalation in phase 1 progressed through 3 cohorts until 2 of 6 patients experienced dose-limiting toxicity or a dose of 5 mg/kg was reached. Once MTD was established, a 1-sided 1-sample log-rank test at significance level of .1 had 85% power to detect a median survival difference (13.69 vs 18.48 months) with 60 deaths over a 12-month accrual period and an additional 18 months of follow-up. OS and PFS were estimated using the Kaplan-Meier method. Results: In phase 1, 24 patients were enrolled. The MTD established was 5 mg/kg, given intravenously 5 days a week for the first 10 RT fractions, then 3 times a week for the duration of RT. The 7 patients enrolled in the third dose level and the 94 enrolled in phase 2 received this dose. Of these 101 patients, 87 were eligible and evaluable. Median survival time was 15.6 months (95% confidence interval [CI]: 12.9-17.6 months), not significantly different from that of the historical control (P=.36). Median PFS was 7.6 months (95% CI: 5.7-9.6 months). One patient (1%) experienced a grade 5 adverse event possibly related to therapy during the concurrent phase, and none experience toxicity during adjuvant TMZ therapy. Conclusions: Treatment was well tolerated, but median OS did not reach improvement specified by protocol compared to historical control, indicating that the combination of standard RT with TMZ and MGd did not achieve a significant survival advantage.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Analysis of Coupled Bunch Instabilities in the NSLS-II Storage Ring with a 7-cell PETRA-III RF Structure

We studied the coupled-bunch instability driven by a 7-cell PETRA-III cavity structure, which is considered to be installed in the commissioning Phase 1 in the NSLS-II storage ring at an average current of 25mA. For instability threshold calculations we used the parameters of the bare lattice (no DW’s and Landau cavities). The transverse and longitudinal coupled-bunch instabilities can be driven by the higher order modes (HOM’s) of the 7-cell PETRA-III cavity structure. In the case of uniform filling the beam is longitudinally stable, and transversely unstable at zero chromaticity. To increase the transverse instability threshold we studied the stabilizing effect of the slow head-tail instability at positive chromaticity. We assume the slow head tail effect is driven by a broadband resonator impedance. In the case of all RF buckets filled (M=1320 bunches, N=3.1x10 8 particles per bunch) the beam is unstable for values of the chromaticity in the range [0 2]. To increase the damping provided by the slow head-tail effect, we discuss fillings with a larger number of particles per bunch. We analyze uniform filling configurations with M=132 (N=3.1x10 9 ) and M=66 (N=6.2x10 9 ). We also discussed HOM’s frequencies detuning based upon temperature change as a cure of the coupled-bunch instabilities, and proposed working points to make the 7-cell PETRA-III cavity structure stable under coupled-bunch interaction.

36 MATERIALS SCIENCE↗

Critical Fluctuations in Beam-Plasma Systems and Solar Type III Radio Bursts

It is shown that the Langmuir waves are excited similar to critical fluctuations during phase transitions when the negative absorption due to electron beam traveling radially outward in the solar atmosphere is balanced by the positive absorption due to collisions in the corona and due to scattering on electron density inhomogeneities in the interplanetary medium. The effective temperature of the Langmuir fluctuations range from 1011 to 1013 K, explaining the majority of the type III bursts. The Rayleigh scattering and direct coupling due to density gradient as well as due to density inhomogeneities are discussed in the context of fundamental radiation and the combination scattering for second harmonic. The number density of electrons in type III beams is estimated and compared with observations. It is also shown that the stabilization of type III beams is achieved automatically since the instability does not develop in the case of critical fluctuations.

Fluctuations↗