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DOE OSTI2023

Integrating Mercury Concentrations in American Alligators ( Alligator mississippiensis ) with Hunter Consumption Surveys to Estimate Exposure Risk

Mercury is a naturally occurring element but is also considered a widespread contaminant due to global anthropogenic activity. Even in moderate amounts, mercury (Hg) is an established neurotoxin and is associated with a range of adverse outcomes both in humans and wildlife. Humans in the United States are most commonly exposed to Hg through contaminated food or drinking water, and the consumption of game species, particularly those occupying higher trophic levels, has the potential to expose hunters to high concentrations of Hg. In the present study, we determined Hg concentrations in tail muscle and blood from American alligators (Alligator mississippiensis) inhabiting a region (Savannah River Site, SC, USA) with known Hg contamination. We then integrated these data with alligator harvest records and previously published surveys of alligator meat consumption patterns to estimate potential exposure risk. We found that the average Hg concentrations in tail muscle (1.34 mg/kg, wet wt) from sampled alligators exceeded the recommended threshold for Hg exposure based on the World Health Organization's guidelines (0.5mg/kg, wet wt). In addition, based on regional consumption patterns reported for both adults and children, we estimated Hg exposures (x¯ Adult = 0.419 μg/kg/day, x¯ Child = 2.24 μg/kg/day) occurring well above the US Environmental Protection Agency methylmercury reference dose of 0.1 μg/kg/day. Although the two reservoirs sampled in the present study are not currently open to alligator hunting, they are connected to waters that are publicly accessible, and the extent of alligator mobility across these sites is not known. Together, the findings reported in the present study further demonstrate the need for active monitoring of Hg concentrations in game species, which can convey substantial exposure risks to the public.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

SPIO‐Au core–shell nanoparticles for promoting osteogenic differentiation of MC3T3‐E1 cells: Concentration‐dependence study

Abstract This work aims to explore the concentration‐dependence of SPIO‐Au core–shell nanoscale particles (NPs) (17.3 ± 1.2 nm in diameter) on biocompatibility and osteogenic differentiation of preosteoblast MC3T3‐E1 cells. The stability of NPs was first investigated by UV–vis absorption spectra and zeta potential measurement. Then concentration effects of NPs (1–80 μg/mL) were evaluated on viability, morphology, proliferation, cellular uptake, and alkaline phosphate (ALP) activity levels. Results have shown strong stability and no acute toxicity (viability > 93%) or morphological difference at all concentration levels of NPs. The proliferation results indicated that the concentration of NPs below 40 μg/mL does not affect the cell proliferation for 7 days of incubation. Transmission electron microscopy images revealed the successful internalization of NPs into MC3T3‐E1 cells and the dose‐dependent accumulation of NPs inside the cytoplasm. The ALP level of MC3T3‐E1 cells was improved by 49% (of control) after treated with NPs at 10 μg/mL for 10 days, indicating their positive effect on early osteogenic differentiation. This study confirmed the excellent biocompatibility of SPIO‐Au NPs and their great potential for promoting osteogenic differentiation and promised the future application for these NPs in bone engineering including drug delivery, cell labeling, and activity tracking within scaffolds. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 3350–3359, 2017.

Yuan, Muzhaozi↗

DOE OSTI2018

Wafer integrated micro‐scale concentrating photovoltaics

Abstract A novel micro‐scale photovoltaic concept, Wafer Integrated Micro‐scale Photovoltaics (WPV), is proposed, analyzed, and experimentally demonstrated. The WPV concept seamlessly integrates multijunction micro‐cells with a multi‐functional silicon platform that simultaneously provides optical concentration, hybrid PV/CPV architecture, and mechanical alignment features. Fabrication and optical performance characterization of the Si platform are described in this paper. Over 100% improvement in the concentration‐acceptance‐angle product ( CAP ) is demonstrated using the wafer‐embedded micro‐concentrating elements, leading to significantly reduced module material and fabrication costs, sufficient angular tolerance for low‐cost trackers, and an ultra‐compact optical architecture compatible with commercial flat panel infrastructures. The development of a prototypical module with a 400× concentration ratio is described. Outdoor optical characterization of the module shows acceptance angles of ±1.7° and ±2.5° for 90% of on‐axis power and full‐width‐half‐maximum, respectively. The projected performance of the PV/CPV hybrid architecture illustrates its potential for cost‐effective collection of both direct and diffuse sunlight, thereby extending the geographic and market domains for cost‐effective PV system deployment. Leveraging low‐cost micro‐fabrication and high‐level integration techniques, the WPV approach presents a promising route to combine the high performance of multijunction solar cells and the low costs of flat‐plate Si PV systems.

Li, Duanhui↗

DOE OSTI2020

Molar Absorptivities of U(VI), U(IV), and Pu(III) in Nitric Acid Solutions of Various Concentrations Relevant to Developing Nuclear Fuel Recycling Flowsheets

Testing of a co-decontamination (CoDCon) tributyl phosphate (TBP) based solvent extraction flowsheet is being performed to optimize conditions for achieving a target U/Pu ratio in the Pu-containing product. The flowsheet is designed to directly produce a mixture of U and Pu with a U/Pu mass ratio of 7/3. The system is monitored in real time using optical spectroscopy, which allows for control of the U/Pu ratio in the aqueous U/Pu nitrate product. On-line spectrophotometric monitoring of the aqueous stream at the reductive stripping step involves determination of U(VI), U(IV) and Pu(III) concentrations and relies on molar absorptivities of these species in nitric acid at a number of wavelengths corresponding to their peaks’ maxima. The magnitudes of these molar absorptivities are a sensitive function of nitric acid concentration and have to be determined as precisely as possible using an off-line spectrophotometry under well controlled conditions. This step (called training set acquisition) is typically performed not in a high contamination area of radiological glovebox where flow-through cells and other on-line equipment are installed but in a less aggressive environment of a radiological fume hood with much better control of stock solutions quality, dilution factors, optical absorbance scale calibration, etc. This is followed by the calibration transfer between the off-line instrument and the instrument deployed during extraction and stripping runs. This paper reports values of molar absorptivities of U(VI), U(IV), and Pu(III) in nitric acid solution of 0.5 M to 4 M concentration and compares them with available technical literature data. Results of off-line spectrophotometric analysis of selected aqueous grab samples from one of CoDCon runs show satisfactory agreement with total uranium and plutonium concentrations determined in the same samples by ICP-MS.

Sinkov, Sergey I.↗

DOE OSTI2019

Visible-enhanced silver-doped PbI{sub 2} nanostructure/Si heterojunction photodetector: effect of doping concentration on photodetector parameters

This paper presents the effect of doping concentration on the properties of PbI{sub 2} nanostructure film and p-PbI{sub 2}:Ag/n-Si photodetector prepared by pulsed laser deposition PLD method. The PbI{sub 2} film was doped with silver at doping concentrations of 1%, 3% and 5%. XRD results show that all deposited PbI{sub 2} films are polycrystalline and well-crystallized along (001) plane with hexagonal structure. The structural studies revealed that the grain size of the film decreases as the doping concentration increase. Energy dispersive X-ray EDX, scanning electron microscope SEM and elemental mapping analysis confirm the presence of Pb, I and Ag elements and the films were near stoichiometric. Raman spectra of PbI{sub 2} film showed the presence of Raman peaks located at 73, 94.3, 108, 165.7, and 208.9 cm{sup −1} corresponding to E{sub 2}{sup 1}, A11, A{sub 1}{sup 2}, 2E{sub 1}{sup 1} and 2A{sub 1}{sup 2} vibration modes, respectively, and a Raman peak at 185 cm{sup −1} was observed for the film doped with 5 wt% which indexed to 2E{sub 1}{sup 1}. The optical energy gap of the film decreased from 2.8 to 2.3 eV after doping with silver. Hall measurement confirms that the deposited PbI{sub 2} films are p-type and the electrical resistivity of the film increases from 1.1 × 10{sup 4} to 1.8 × 10{sup 7} Ω cm as doping concentration increases from 1 to 5%.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2024

Variation of the Passive Film on Compositionally Concentrated Dual-Phase Al 0.3 Cr 0.5 Fe 2 Mn 0.25 Mo 0.15 Ni 1.5 Ti 0.3 and Implications for Corrosion

The passive film on a dual-phase Al 0.3 Cr 0.5 Fe 2 Mn 0.25 Mo 0.15 Ni 1.5 Ti 0.3 FCC + Heusler (L2 1 ) compositionally concentrated alloy formed during extended exposure to an applied potential in the passive range in dilute chloride solution was characterized. Each phase, with its own distinct composition of passivating elements, formed unique passive films separated by a heterophase interface. High-resolution, surface sensitive characterization enabled chemical analysis of the passive film formed over individual phases. The film formed over the L2 1 phase had a higher concentration of Al, Ni, and Ti, while the film formed over FCC phase was of similar thickness but contained comparatively higher Cr, Fe, and Mo concentrations, consistent with the differences in bulk microstructure composition. The passive film was continuous across phase boundaries and the distribution of passivating elements (Al, Cr, and Ti) indicated both phases were independently passivated. Spatially resolved analysis of the surface chemistry of the dual-phase CCA revealed that the cation with the highest composition in passive film formed on the FCC phase was Cr (52.4 at. pct) and for the L2 1 phase was Ti (53.1 at. pct) despite the bulk concentration of each element being below 20 at. pct in their respective phases. Al, Cr, and Ti were enriched in both phases within the passive film relative to their respective bulk compositions. In parallel studies, single-phase alloys with compositions representative of the FCC and L2 1 phases were synthesized to evaluate the corrosion behavior of each phase in isolation. The corrosion behavior of the dual-phase alloy showed passivity evidenced by a pitting potential of 0.615 V SCE in 0.01 M NaCl. The pitting potential and other electrochemical parameters suggested a combination of behaviors of both single-phase samples, suggesting that the global corrosion behavior may be represented by a composite theory applied to phases, their area fractions, and interphase length. However, the interphase in the dual-phase CCA was a local corrosion initiation site and may limit localized corrosion protectiveness. The alloy design implications for optimization of second phase structure and morphology are discussed.

36 MATERIALS SCIENCE↗

DOE OSTI2018

Plasma Electrolytic Oxidation Coatings on Pure Ti Substrate: Effects of Na{sub 3}PO{sub 4} Concentration on Morphology and Corrosion Behavior of Coatings in Ringer’s Physiological Solution

Plasma electrolytic oxidation has been used as a relatively new method for applying ceramic coatings having different features. In the present study, commercially pure titanium is used as substrate, and effects of trisodium phosphate electrolyte concentration on the microstructure, as well as corrosion behavior of the coating in Ringer’s physiological solution are investigated. The morphology and phase compositions of coatings were analyzed by using scanning electron microscopy (SEM) and x-ray diffraction patterns. The study on the corrosion behavior of samples in a Ringer’s physiological solution was carried out using open-circuit potential potentiodynamic polarization and electrochemical impedance spectroscopy. The results of electrochemical analysis proved that higher concentration of phosphate electrolyte leads to increase in the corrosion resistance of applied coatings. Accordingly, obtained results revealed that the optimum electrolyte concentration for the best corrosion behavior was 20 g L{sup −1}. Furthermore, SEM images and reduction in the dielectric breakdown potential indicated that increase in the electrolyte concentration leads to morphological improvement and smoothening of the surface.

36 MATERIALS SCIENCE↗

DOE OSTI2019

Effect of Carbon Nanotube Concentration on the Corrosion Behavior of Electroless Ni-B-CNT Coating

In this study, Ni-B-CNT composite was deposited on AISI 4140 steel using different concentrations of CNTs ranging from 0.2 to 1 gr/lit in an electroless bath. The phase analysis and surface morphology of the samples were characterized using x-ray diffraction and FESEM. The corrosion behavior of the coated samples was investigated in a 3.5 wt.% NaCl solution through potentiodynamic polarization, EIS, and electrochemical noise (EN) analyses. The corroded surface of the samples was further analyzed via FESEM observation after 10 days of immersion in corrosive medium. It was found that although adding 0.2 gr/lit CNT in electroless solution improves corrosion resistance, increasing CNT concentration from 0.2 up to 1 gr/lit increases the corrosion rate. The FESEM observations and EN results imply that the formation of micro-galvanic cells in samples with high concentration of CNTs leads to nucleation and growth of the pits. The results revealed that no passive layer was formed on the surface of the Ni-B sample, and the corrosion occurred through ionic diffusion into the cracks and crevices. The results of potentiodynamic test show that adding CNTs into electroless bath facilitates the formation of passive layer. However, results of EN test imply that increasing CNT concentration causes repetitive breakdown and recovery of passive film.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Change of Electrical and Transport Properties of Nickel Oxide by Carrier Concentration and Temperature through First-Principle Calculations

Abstract Nickel is typically used as one of the main components in electrical contact devices or connectors. Nickel oxide (NiO) is usually formed on the surfaces of electrodes and can negatively impact system performance by introducing electrical contact resistance. The thermal, electrical, and transport properties of NiO, as a Mott insulator or a p-type semiconductor, can be altered by operating and environmental conditions such as temperature and stress/strain by contact. In this study, we investigate the fundamental material properties of NiO through the first-principle calculations. First, we obtain and compare the lattice parameter, magnetic moment, and electronic structure for NiO via the WIEN2K simulations with four different potentials (i.e., GGA, GGA + U, LSDA, and LSDA + U). Then, using the WIEN2K simulation results with LSDA + U potential that produces a highly accurate bandgap for NiO, we calculate the electrical conductivity and electrical part of the thermal conductivity of nickel and NiO as a function of temperature and carrier concentration through the BoltzTraP simulations. Systematic simulation results revealed that the electrical conductivity relative to the relaxation time for NiO increases with the carrier concentration, while it shows a slightly decreasing trend with temperature under a fixed carrier concentration. By contrast, the electrical part of the thermal conductivity shows an increasing trend considering carrier concentration and temperature.

Shah, Nayem Md. Reza↗

DOE OSTI2019

The Occurrence and Concentration of Rare Earth Elements in Acid Mine Drainage and Treatment By-products: Part 1—Initial Survey of the Northern Appalachian Coal Basin

The conventional rare earth element (REE) industry has historically sought to develop ore deposits where geologic processes have produced mineralized zones with commercially attractive REE concentrations. These deposits are extremely uncommon, particularly in the USA. Given the criticality of these materials and the need for sustainable domestic supply, the current research seeks to leverage other autogenous processes that lead to concentrated REE resources. One such process is the generation of acid mine drainage (AMD). AMD is very common in many coal mining districts and results from the exposure and oxidation of pyrite during mining. During the generation and migration of AMD, liberated sulfuric acid mobilizes several metal ions including REEs. Treatment of AMD is required under U.S.C §1251, the Clean Water Act, and often consists of neutralization, oxidation, and metal hydroxide precipitation. To investigate the deportment of REEs during this process, a field sampling campaign was undertaken, whereby the concentration of REEs in AMD and AMD precipitates was measured directly. In the nine sites evaluated in this study, the REE concentrations of the precipitates varied from 29 to 1286 ppm with an average of 517 ppm among the sampled sites. The individual elements were enriched compared with the associated bulk Northern Appalachian (NAPP) coal material by factors ranging from 3 to 15. Furthermore, the distribution of REEs in all precipitate samples favored the heavy REEs (HREEs) when compared with traditional REE ores. Finally, this research represents the first part of multi-part research endeavor to characterize, classify, and determine the practicality of refining REEs from AMD and its by-products.

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2021

Experimental and numerical study of the effects of solution concentration and temperature on concrete under external sulfate attack

The work reports on an experimental programme, conducted to validate comprehensively our previously proposed coupled chemo-transport model for external sulfate attack on concrete. Specifically, the effects of the concentration of sulfate solution and temperature on the distribution of sulfate ions in concrete are experimentally investigated and used to demonstrate the accuracy of the modeling framework. Further, the profile of aluminate depletion and the leaching depth numerically are investigated. For all cases the model predictions are in good agreement with the experimental results, showing increases of the concentration of sulfate ions in concrete with higher concentrations of sulfate solution and higher temperatures. It is concluded that higher sulfate solution concentration and temperature enhance the processes involved in the external sulfate attack on concrete, namely diffusion of sulfate ions and their chemical reactions with concrete. It is found that these parameters affect the external sulfate attack predominantly via the chemical reaction process.

36 MATERIALS SCIENCE↗

DOE OSTI2018

Seasonal differences in trace element concentrations and distribution in Spartina alterniflora root tissue

This study uses nanometer-scale synchrotron X-ray nanofluorescence to investigate season differences in concentrations and distributions of major (Ca, K, S and P) and trace elements (As, Cr, Cu, Fe and Zn) in the root system of Spartina alterniflora collected from Jamaica Bay, New York, in April and September 2015. The root samples were cross-sectioned at a thickness of 10 μm. Selected areas in the root epidermis and endodermis were mapped with a sampling resolution of 100 and 200 nm, varying with the mapping areas. The results indicate that trace element concentrations in the epidermis and endodermis vary among the elements measured, possibly because of their different chemical properties or their ability to act as micronutrients for the plants. Elemental concentrations (As, Ca, Cr, Cu, Fe, K, P, S and Zn) within each individual root sample and between the root samples collected during two different seasons are both significantly different (p < 0.01). Furthermore, this study indicates that the nonessential elements (As and Cr) are significantly correlated (p < 0.01) with Fe, with high concentrations in the root epidermis, while others are not, implying that Fe may be a barrier to nonessential element transport in the root system. Hierarchy cluster analysis shows two distinct groups, one including As, Cr and Fe and the other the rest of the elements measured. Factor analysis also indicates that the processes and mechanisms controlling element transport in the root system can be different between the nutrient and nonessential elements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

PyDII: A python framework for computing equilibrium intrinsic point defect concentrations and extrinsic solute site preferences in intermetallic compounds

Point defects play an important role in determining the structural stability and mechanical behavior of intermetallic compounds. To help quantitatively understand the point defect properties in these compounds, we developed PyDII, a Python program that performs thermodynamic calculations of equilibrium intrinsic point defect concentrations and extrinsic solute site preferences in intermetallics. The algorithm implemented in PyDII is built upon a dilute-solution thermodynamic formalism with a set of defect excitation energies calculated from first-principles density-functional theory methods. The analysis module in PyDII enables automated calculations of equilibrium intrinsic antisite and vacancy concentrations as a function of composition and temperature (over ranges where the dilute solution formalism is accurate) and the point defect concentration changes arising from addition of an extrinsic substitutional solute species. To demonstrate the applications of PyDII, we provide examples for intrinsic point defect concentrations in NiAl.

36 MATERIALS SCIENCE↗

DOE OSTI2019

Dye doped concentric shell nanoparticles for enhanced photophysical performance of downconverting light emitting diodes

In this study, we examined the potential for perylene dye doped nanoparticles to enhance Light Emitting Diodes (LED) efficacy by minimizing π–π intermolecular aggregation, and enhancing photoluminescence and photostability of the dye molecules in the solid state. Towards this end, we encapsulated perylene dyes, suitably modified with a reactive silica precursor, into silica nanoparticles within a silica-dye-silica concentric layered shell. We found that the fluorescent yield was higher when the dye was embedded in a buried concentric shell within the silica nanoparticles (NPs) compared to an undoped shell/dye doped core nanoparticle morphology or unencapsulated dye with the same net dye concentration in solution. A strong dependence of relative quantum yield on dye doping concentration in the silica-dye-silica nanoparticles was observed. The uniform ~ 100 nm large silica-dye-silica layered nanoparticles were used to prepare transparent dye doped silica nanoparticle/silicone nanocomposites. Dye doped silica nanoparticle/silicone nanocomposites exhibited higher photostability than the unencapsulated dye samples during long time aging tests under a blue LED with a wavelength of 455 nm at 300 ± 3% mA for 24 h. Novel dye doped layered silica NPs and their nanocomposites offer scope for developing organic luminescent materials into efficient and color-tunable light emitters for low-cost display, lighting, and optical communication applications.

42 ENGINEERING↗

DOE OSTI2019

Europium concentration effects on the scintillation properties of Cs 4 SrI 6 :Eu and Cs 4 CaI 6 :Eu single crystals for use in gamma spectroscopy

Recently discovered scintillators Cs 4 SrI 6 :Eu and Cs 4 CaI 6 :Eu have shown promising properties for gamma-ray detection in homeland security applications, with <4% energy resolution (at 662 keV) and light yields above 50,000 ph/MeV. However, a thorough investigation of the effects of europium concentration has not yet been conducted. In this work, Eu 2+ concentration was varied from 0.5 mol% to 9 mol%, and Ø7 mm single crystals were grown from the melt via the vertical Bridgman method. Scintillation performance was evaluated as a function of Eu 2+ concentration to determine the optimal amount. The observed trend was improved energy resolution and higher light yield with increasing Eu 2+ concentration up to 7 mol%. The best energy resolution achieved was 3.2% for Cs 4 SrI 6 :Eu 7% and 3.6% for Cs 4 CaI 6 :Eu 7%. Their respective light yields were 71,000 ph/MeV and 69,000 ph/MeV.

36 MATERIALS SCIENCE↗

DOE OSTI2014

Local composition and carrier concentration in Pb0.7Ge0.3Te and Pb0.5Ge0.5Te alloys from 125Te NMR and microscopy

Pb0.7Ge0.3Te and Pb0.5Ge0.5Te alloys, (i) quenched from 923 K or (ii) quenched and annealed at 573 K for 2 h, have been studied by 125Te NMR, X-ray diffraction, electron and optical microscopy, as well as energy dispersive spectroscopy. Depending on the composition and thermal treatment history, 125Te NMR spectra exhibit different resonance frequencies and spin-lattice relaxation times, which can be assigned to different phases in the alloy. Quenched and annealed Pb0.7Ge0.3Te alloys can be considered as solid solutions but are shown by NMR to have components with various carrier concentrations. Quenched and annealed Pb0.5Ge0.5Te alloys contain GeTe- and PbTe-based phases with different compositions and charge carrier concentrations. Based on the analysis of non-exponential 125Te NMR spin-lattice relaxation, the fractions and carrier concentrations of the various phases have been estimated. Our data show that alloying of PbTe with Ge results in the formation of chemically and electronically inhomogeneous systems. 125Te NMR can be used as an efficient probe to detect the local composition in equilibrium as well as non-equilibrium states, and to determine the local carrier concentrations in complex multiphase tellurides.

36 MATERIALS SCIENCE↗

DOE OSTI2013

Influence of temperature and precursor concentration on the synthesis of HDA-capped Ag{sub 2}Se nanoparticles

Graphical abstract: The temperature effect on the growth and size of silver selenide nanoparticles with the size distribution and XRD patterns. Highlights: ► The HDA-capped Ag{sub 2}Se nanoparticles were synthesized via the colloidal route. ► Temperature and monomer concentration of the reaction were varied. ► The concentration as a factor influenced particles with a decrease observed as the amount of Ag{sup +} ion source is increased. ► Temperature has expected influence on the growth of particles resulting in increase as the temperature is increased. ► TEM images shows spherical particles and their orthorhombic phase from structural analysis by XRD. - Abstract: The size dependent of temperature and precursor concentration on the synthesis of hexadecylamine capped Ag{sub 2}Se nanoparticles via the colloidal route were studied using the combination of optical and structural analysis. The as-prepared Ag{sub 2}Se nanoparticles showed the quantum confinement with all the obtained absorption band edges blue-shifted from the bulk and their corresponding emission maxima displaying a red-shift from band edges characterised by UV–vis absorption and photoluminescence spectroscopy. The particle sizes were obtained from transmission electron microscopy analysis. The increase in precursor concentration resulted in a decrease in nanoparticle sizes. The increase in reaction temperature showed an increase in the nanoparticle sizes, when the critical temperature at 160 °C was reached, the nanoparticle sizes decreased.

36 MATERIALS SCIENCE↗

DOE OSTI2023

The apparent reversal of the Law of Mass Action in concentrated multicomponent aqueous solutions

Although it is well known that aqueous electrolyte solutions behave non-ideally, few are so non-ideal that adding an electrolyte to a saturated solution with a common ion enhances rather than depresses solubility. Nonetheless, this apparent reversal of the Law of Mass Action (LMA) has been observed in simple nitrate solutions at high concentrations. A leading hypothesis is that ion clusters are formed and stabilized by ions having different charge densities. We report the present study examines this concept, in part by reviewing relevant data from multicomponent aqueous solutions containing sodium nitrate (NaNO 3 ), sodium nitrite (NaNO 2 ), sodium hydroxide (NaOH), and sodium aluminate (NaAl(OH) 4 ) - the major constituents in alkaline nuclear waste. Here, NaOH and NaAl(OH) 4 did not enhance the solubility of NaNO 3 or NaNO 2 , whereas NaNO 2 and NaNO 3 enhanced rather than depressed the solubility of each other despite each having the sodium cation (Na + ) in common. Solutions evaluated in this study have more than 20 molal total Na + concentration, and most have less than one mole of water per mole of ion. Thus, this reversal of the LMA occurs in solutions where there is not enough water to fully hydrate the ions, pointing to the importance of ion cluster formation. Within the composition range of the solutions analyzed here, this reversal of the LMA occurs regardless of NaAl(OH) 4 and NaOH concentrations. Elevated temperatures also result in the reversal of the LMA in the subsystems NaNO 2 -NaNO 3 -H 2 O and NaOH-NaNO 3 -H 2 O, consistent with spectroscopic and computational studies showing enhanced interactions at higher temperatures. Although speciation in these highly concentrated electrolyte solutions is not well understood, the stabilization of ion clusters by: (i) optimizing charge density around the ions through different combinations of mixed cations and anions in solution; and (ii) high temperatures where ions experience prolonged contact, offers important clues for future research into how these species control solubility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗