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Archaeological glasses with prolonged exposure to biogeochemical processes in the environment can be used to understand glass alteration, which is important for the safe disposal of vitrified nuclear waste. Samples of mafic and felsic glasses with different chemistries, formed from melting amphibolitic and granitoid rocks, were obtained from Broborg, a Swedish Iron Age hillfort. Glasses were excavated from the top of the hillfort wall and from the wall interior. A detailed microscopic, spectroscopic, and diffraction study of surficial textures and chemistries were conducted on these glasses. Felsic glass chemistry was uniform, with a smooth surface showing limited chemical alteration (

The complex distribution of particle charge states resulting from neutralization processes by radioactive or soft X-ray charge neutralizers is a well-documented problem in aerosol science. Here, we demonstrate that non-idealities in the collection efficiency of an impactor allows for the transmission of an unexpected population of multiply charged particles by a differential mobility analyzer that can bias optical measurements. The extinction cross sections (Cext) of ammonium sulfate particles were quantified using cavity ring-down spectroscopy and particle counting. Particles were selected by electrical mobility (i.e., a metric of particle size) using a differential mobility analyzer (DMA) or electrical mobility and mass selected by a tandem DMA and aerosol particle mass analyzer (APM), respectively, to elucidate multiple charging artifacts. Measured Cext exhibited statistically significant differences at particle sizes near the impactor cut point implying that these multiply charged particles should not be present and could not be confirmed by parallel size distribution measurements. Additionally, comparison of Cext with Mie theory demonstrates that misclassification of the multiply charged particles can give rise to numerically accurate results. To understand these observations, the collection efficiency (CE) of four impactors from similar electrostatic classifiers was investigated. From these measurements, it was determined that the nominal and actual diameters of the impactors differed by −0.5% (457 μm vs. (455 ± 1) μm, respectively (uncertainty is 1σ standard deviation)) but the average Stk50 (the Stokes number at the cut-point, D50) values differed by ≈ 23% (0.23 vs. 0.18 ± 0.01, respectively). The measured CE as a function of √Stk (a metric of particle aerodynamic size) exhibits a long tail toward higher √Stk values, allowing for transmission of the larger and multiply charged particles observed in the optical measurements. These measurements highlight the utility of using orthogonal, spectroscopic methods to quantify the presence of multiply charged particles. Copyright © 2023 American Association for Aerosol Research

Because microbes cannot be eliminated from radioactive waste disposal facilities, the consequences of bio-colonization must be understood. At a pre-Viking era vitrified hillfort, Broborg, Sweden, a...

To realize high specific capacity Li-metal batteries, a protection layer for the Li-metal anode is needed. We are carrying out combinatorial screening of Li-alloy thin films as the protection layer...

Dilute aqueous pertechnic acid has long been known as strong monoprotic acid that behaves as a simple pertechnetate ion in aqueous solution. As pertechnic acid concentrates by evaporation, it becomes yellow and then dark red, and dark-red crystalline material may ultimately be obtained. We show that as pertechnic acid concentrates, at least three compounds are formed: a yellow viscous liquid, a colorless (not red) crystalline solid, and a small amount of an intensely colored red-purple compound. The colorless crystalline compound melts at 118 °C and can be melted and recrystallized several times with little decomposition. The red-purple compound is apparently not stable at room temperature and quickly decomposes if it is isolated. UV-vis spectra show that Beer's law does not hold as pertechnic acid concentrates by evaporation. We report densities, 99Tc nuclear magnetic resonance spectra, and ultraviolet-visible absorption spectra for highly pure aqueous pertechnic acid (accompanied by the other technetium compounds that form) ranging from 1 to 14 M in technetium concentration.

Understanding the chemical durability of neutron shielding materials is necessary when assessing their long-term service potential. In this study, the chemical durability of a 6Li enriched neutron shielding glass that has been exposed to natural, near-operational conditions is assessed by Prompt Gamma Activation Analysis (PGAA) and Neutron Depth Profiling (NDP). These non-destructive, nuclear analysis techniques are sensitive to 6Li, and PGAA is uniquely able to detect H in low quantities in solids. It was determined that the enriched alumino-silicate glass can alter within 2 months of exposure to the natural environment. This exposure resulted in an average surface alteration layer thickness of ≈22 μm. The alteration layer contained ≈47% less 6Li than the bulk glass. Alternatively, a 3 years exposed sample of the glass had a surface alteration depth of ≈30 μm and 6Li depletion levels in the alteration layer were between 47% and 75% less 6Li than the bulk glass. When the alteration layer on the 3 years sample was removed, the H content of the glass's surface was nearly eliminated. This sample also showed variable Li concentrations throughout the alteration volume, which contrasts with near static Li concentration in the alteration volume of the 2 months sample. From these findings it was determined that the depletion in Li at the surface of the glass will not affect the glass's neutron shielding properties, but it may change the mechanical stability of the glass's surface and, due to increased H content in the alteration layer, make it an inappropriate material for the lining of certain neutron analysis instruments.

Glass alteration in the presence of microorganisms has been a topic of research for over 150 years. Researchers from a variety of disciplines, including material science, biology, chemistry, geology, physics, and cultural heritage materials preservation have conducted experiments in this area to try and understand when, how, and why microorganism may interact and subsequently influence the alteration of glass. The breadth and depth of these studies are the topic of this review. This review presents a detailed history and a comprehensive overview of this field of research, while maintaining focus on the terrestrial alteration of anthropogenic silicate glasses. Within this manuscript is a schema for bio-interaction with silicate glasses and an outline of an evidence-based hypothesis on how these interactions may influence glass alteration processes. Topics discussed include microbial colonization of glass, development, and interactions of biofilms with glass surface, abiotic vs. biotic alteration processes, and signatures of bio-alteration. Future research needs and a discussion of practical drivers for this research are summarized.

Under high humidity conditions that mimic respiration, the filtration efficiency (FE) of hydrophilic fabrics increases when challenged with hygroscopic nanoparticles, for example, respiratory droplets containing SARS-CoV-2. The FE and differential pressure (ΔP) of natural, synthetic, and blended fabrics were measured as a function of relative humidity (RH) for particles with mobility diameters between 50 and 825 nm. Fabrics were equilibrated at 99% RH, mimicking conditions experienced when worn as a face mask. The FE increased after equilibration at 99% RH by a relative percentage of 33 ± 12% for fabrics composed of two layers of 100% cotton when challenged by 303 nm-mobility-diameter NaCl aerosol. The FE for samples of synthetics and polyester/cotton blends was unchanged upon equilibration at 99% RH. Increases in FE for 100% cotton fabrics were a function of particle size with a relative increase of 63% at the largest measured particle size (825 nm). The experimental results are consistent with increased particle capture due to H2O uptake and growth as the particles traverse the fabric.

Filtration efficiency (FE), differential pressure (ΔP), quality factor (QF), and construction parameters were measured for 32 cloth materials (14 cotton, 1 wool, 9 synthetic, 4 synthetic blends, and 4 synthetic/cotton blends) used in cloth masks intended for protection from the SARS-CoV-2 virus (diameter 100 ± 10 nm). Seven polypropylene-based fiber filter materials were also measured including surgical masks and N95 respirators. Additional measurements were performed on both multilayered and mixed-material samples of natural, synthetic, or natural-synthetic blends to mimic cloth mask construction methods. Materials were microimaged and tested against size selected NaCl aerosol with particle mobility diameters between 50 and 825 nm. Three of the top five best performing samples were woven 100% cotton with high to moderate yarn counts, and the other two were woven synthetics of moderate yarn counts. In contrast to recently published studies, samples utilizing mixed materials did not exhibit a significant difference in the measured FE when compared to the product of the individual FE for the components. The FE and ΔP increased monotonically with the number of cloth layers for a lightweight flannel, suggesting that multilayered cloth masks may offer increased protection from nanometer-sized aerosol with a maximum FE dictated by breathability (i.e., ΔP).

Models for long-term glass alteration are required to satisfy performance predictions of vitrified nuclear waste in various disposal scenarios. Durability parameters are usually extracted from short-term laboratory tests, and sometimes checked with long-term natural experiments on glasses, termed analogues. In this paper, a unique potential ancient glass analogue from Sweden is discussed. The hillfort glass found at Broborg represents a unique case study as a vitrified waste glass analogue to compare to Low Activity Waste glass to be emplaced in near surface conditions at Hanford (USA). Glasses at Broborg have similar and dissimilar compositions to LAW glasses, allowing the testing of long-term alteration of different glass chemistries. In addition, the environmental history of the site is reasonably well documented. Initial investigations on previously collected samples established methodologies for handling and characterizing these artifacts by laboratory methods while preserving their alteration layers and cultural context. Evidence of possible biologically influenced glass alteration, and differential alteration in the 2 types of glass found at the Broborg site is presented.

Though not often discussed explicitly in literature, sample handling and preparation for advanced characterization techniques is a significant challenge for radiological materials. In this contribution, a detailed description is given of method development associated with characterization of highly radioactive and, in some cases, hygroscopic oxides of technetium. Details are given on developed protocols, fixtures, and tooling designed for x-ray and neutron diffraction, x-ray absorption, Raman spectroscopy, magic angle spinning nuclear magnetic resonance, and electron paramagnetic resonance. In some cases, multiple iterations of improved sample holder design are described. Lessons learned in handling Tc compounds for these and similar characterization methods are discussed.

We report on the influence of Fe2O3 on the crystallization kinetics of nepheline (Na2O·Al2O3·2SiO2)-based sodium aluminosilicate glasses. A series of glasses with varying Al2O3/Fe2O3 content were synthesized in the system 25Na2O–(25–x) Al2O3–xFe2O3–50SiO2 (x varies between 0 and 5 mol%) through melt-quench technique. A systematic set of experiments were performed to elucidate the influence of iron speciation (Fe2+/Fe3+) on the crystallization kinetics of these glasses including: (1) obtaining the details of nonisothermal crystallization kinetics by differential scanning calorimetry, (2) determining the influence of heat treatment on the structure and iron coordination in glasses by X-ray photoelectron spectroscopy and wet chemistry, and (3) following the crystalline phase evolution in glasses in air and inert environments by X-ray diffraction and scanning electron microscopy. The crystallization of two polymorphs of NaAlSiO4—carnegieite (orthorhombic) and nepheline (hexagonal)—was observed in all the glasses, wherein the incorporation of iron promotes the formation of nepheline over carnegieite while shifting the crystallization mechanism from surface to volume. The influence of environment (air versus inert) and iron content on the crystallization kinetics of these glasses is contextualized from the perspective of the devitrification problem usually observed in sodium- and alumina-rich high level nuclear waste glasses.

A spectroscopic study was conducted on six simulant nuclear waste glasses using multi-nuclear NMR, Raman, and Mossbauer spectroscopies exploring the role of Si, Al, B, Na, and Fe in the glass network with the goal of understanding melt structure precursors to deleterious nepheline crystal formation. NMR showed two sites each for Al, Si, and Na in the samples which crystallized significant amounts of nepheline, and B speciation changed, typically resulting in more B(IV) after crystallization. Raman spectroscopy suggested that some of the glass structure is composed of metaborate chains or rings, thus significant numbers of non-bridging oxygen and a separation of the borate from the alumino-silicate network. Mossbauer, combined with Fe redox chemical measurements, showed Fe playing a minor role in these glasses, mostly as Fe3 +, but iron oxide spinel forms with nepheline in all cases. A model of the glass network and allocation of non-bridging oxygens (NBOs) was computed using experimental B(IV) fractions which predicted a large amount of NBO consistent with Raman spectra of metaborate features.

Insight into the solid-state chemistry of pure technetium-99 (99Tc) oxides is required in the development of a robust immobilization and disposal system for nuclear waste stemming from the radiopharmaceutical industry, from the production of nuclear weapons, and from spent nuclear fuel. However, because of its radiotoxicity and the subsequent requirement of special facilities and handling procedures for research, only a few studies have been completed, many of which are over 20 years old. In this study, we report the synthesis of pure alkali pertechnetates (sodium, potassium, rubidium, and cesium) and analysis of these compounds by Raman spectroscopy, X-ray absorption spectroscopy (XANES and EXAFS), solid-state nuclear magnetic resonance (static and magic angle spinning), and neutron diffraction. The structures and spectral signatures of these compounds will aid in refining the understanding of 99Tc incorporation into and release from nuclear waste glasses. NaTcO4 shows aspects of the relatively higher el...

Compositional Imaging and Analysis of Late Iron Age Glass from the Broborg Vitrified Hillfort, Sweden

Nuclear waste must be deposited in such a manner that it does not cause significant impact on theenvironment or human health. In some cases, the integrity of the repositories will need to sustain fortens to hundreds of thousands of years. In order to ensure such containment, nuclear waste is frequentlyconverted into a very durable glass. It is fundamentally difficult, however, to assure the validity ofsuch containment based on short-term tests alone. To date, some anthropogenic and natural volcanicglasses have been investigated for this purpose. However, glasses produced by ancient cultures for thepurpose of joining rocks in stonewalls have not yet been utilised in spite of the fact that they might offersignificant insight into the long-term durability of glasses in natural environments. Therefore, a projectis being initiated with the scope of obtaining samples and characterising their environment, as well asto investigate them using a suite of advanced materials characterisation techniques. It will be analysedhow the hillfort glasses may have been prepared, and to what extent they have altered under in-situconditions. The ultimate goals are to obtain a better understanding of the alteration behaviour of nuclearwaste glasses and its compositional dependence, and thus to improve and validate models for nuclearwaste glass corrosion. The paper deals with project planning and initiation, and also presents some earlyfindings on fusion of amphibolite and on the process for joining the granite stones in the hillfort walls.Keywords: ageing, amphibolite, analogue, anthropogenic, Broborg, glass, hillfort, hill-fort, leaching,long-lived, nuclear, rampart, waste. Konferensartikel i tidskrift