Alteration of archeological and natural analogues for radioactive waste glass under different environmental conditions

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Neeway, Eschar Gichon, and 25 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5744111/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 05 Aug, 2025 Read the published version in npj Materials Degradation → Version 1 posted 9 You are reading this latest preprint version Abstract Hundreds of thousands of cubic meters of legacy radioactive waste from plutonium production stored at U.S. Department of Energy’s Hanford site will be immobilized in glass for disposal. The glass must limit radionuclide release into the environment for thousands of years, which is challenging to assess in laboratory experiments. Long-term alteration behavior of analogue glasses can demonstrate how radioactive waste glass will perform over extended periods. Glasses buried for hundreds of years at climatically variable sites were selected for analysis, based on their fulfillment of criteria to be analogues for waste glass. Glass surficial layers were characterized using tomography, SEM, and XRD. The thickness, chemistry and morphology of alteration layers are discussed in terms of sample chemistry and burial conditions. A key finding is that glass in arid environments, e.g., Timna (Israel), exhibits thinner surface layers (~ 2 µm) compared to glass altered in humid conditions, e.g., Dobkowice (Poland) (up to 59 µm), confirming the significant role of environmental factors in glass durability. However, the correlation between sample age and alteration layer thickness was less strong, challenging the assumption that older samples would have more extensive alteration. Newberry (USA) obsidian (1,350 years old) had alteration layers ~ 15 µm, while Broborg (Sweden) glass (1,500 years old) exhibited layers as thin as 8 µm. Quantification of archeological and natural analogue glass alteration upon exposure to variable environmental factors provides a unique insight into long-term glass alteration. These findings support use of glass for radioactive waste disposal at Hanford and are applicable globally to disposal in near surface facilities. Earth and environmental sciences/Environmental sciences/Environmental chemistry/Pollution remediation Physical sciences/Energy science and technology/Nuclear energy/Nuclear waste archeological glasses natural glasses alteration layers radioactive waste disposal Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Figure 12 Figure 13 Figure 14 Figure 15 INTRODUCTION Glass waste forms are required to safely dispose of radioactive waste by immobilizing radionuclides and mitigating their release into the environment. At the Hanford site, a Department of Energy legacy nuclear waste site in Washington state, USA, hundreds of thousands of cubic meters of legacy radioactive waste from plutonium production will be immobilized in glass, with low activity waste (LAW) glass disposed in a near surface integrated disposal facility (IDF). The glass must limit radionuclide release into the environment for thousands of years, which is challenging to assess in laboratory experiments. Central to radioactive waste management is to understand the corrosion processes and quantify the corrosion rates of the glass waste form. However, laboratory glass corrosion experiments have a limitation: their timeframes are considerably shorter than the timeframes over which radionuclides must be retained in a nuclear waste disposal site. Studies of natural analogues 1 – 9 and anthropogenic glasses 10 – 15 can help bridge this important gap. Using such glasses has significant theoretical and practical implications for the field of nuclear waste management. By validating models used to assess waste form behavior with findings from natural and anthropogenic glasses, we can better understand the long-term performance of nuclear waste glasses. The alteration environments for these glass analogues vary in terms of temperature, pore fluid chemistry and pH, solid surface area to liquid volume ratio, percolation rate, and soil microbial communities. These variables must be considered when comparing analogues with proposed nuclear waste glasses. 9 Natural glass analogues such as basaltic glasses (45–50 wt.% SiO 2 ), tektites (65–90% wt.% SiO 2 ), and obsidian glasses (70–75 wt.% SiO 2 ) are found in the terrestrial environment. The thickness of the surface alteration layer can be used to semi-quantitatively evaluate the alteration rate of glasses. 15 , 16 Research suggests that the alteration mechanisms of natural, anthropogenic, and nuclear glasses are similar. 6 Techer et al. 16 compared the alteration of basaltic glass (ages ranging from several thousand to a few million years) in the natural environment with the alteration of basaltic glass and a reference nuclear waste glass (SON68) under laboratory conditions for periods of four days up to several hundred days. Techer et al. 16 pointed out some uncertainties and assumptions for natural samples, for example, the uncertainty in the nature of the altering environment and glass-solution contact time, and the assumption that the palagonite (natural alteration product) thickness can be directly compared to alteration layer thicknesses measured on glasses corroded in laboratory experiments. However, the results suggest that the mean alteration rate estimated from measured palagonite thickness and the age of the natural glasses was comparable to rates measured in closed system laboratory experiments. It was hypothesized that this was due to the alteration products forming a protective layer on the glass surface. 16 Archaeological glasses have also been used as analogues for comparison with nuclear waste glass. 17 While archeological analogues are not compositionally identical to natural and nuclear glasses, they do contain most of the same major elements (alkalis, Si, Al, Fe, etc.). 18 Archaeological glasses also meet the criteria for an analogue because information about the altering environment over the glass’s exposure time is often well documented. For example, two Roman glasses have been used as analogues to study long-term glass alteration behavior: 1) glass from a shipwreck off the coast of the Embiez Islands, France; 12 – 14 2) glass from the shipwreck Iulia Felix off the coast near Grado, Italy. 11 , 19 , 20 These two glasses with similar compositions were altered in marine environments for nearly 1800 years. The Embiez glass was altered in open water in the Mediterranean Sea (15°C). The Iulia Felix glass was altered in the Adriatic Sea (15°C), which has a slightly different chemistry than the Mediterranean, and was covered with sand during its alteration. The Embiez glass shows significant cracking due to fast cooling during its fabrication, and an alteration behavior that is dependent on the size of the cracks. 12 The same cracking phenomenon is observed in nuclear waste glass fabrication. The glass from the Iulia Felix shipwreck contains both colored 19 and colorless fractions. 20 The two glasses have compositions that vary only slightly; however, alteration of the colorless glass results in an opaque white crust, composed mostly of silica (SiO 2 ), while the colored fraction shows alteration layers consisting of repeating lamellae. 21 Lamellae have also been observed in static tests of nuclear waste glass in highly acidic conditions. 22 This type of alteration has not been observed in laboratory testing at pH values near those expected in a disposal facility (pH 6–9), but the pH dependence of this possible dissolution-precipitation mechanism needs to be confirmed. 23 Waste glasses are typically subjected to short-term, accelerated laboratory tests to show they are chemically durable for long periods. The kinetic behavior of these accelerated laboratory tests is then extrapolated over long time periods and may not produce accurate predictions of glass durability over thousands of years. In addition, glass analogues have been used to predict the alteration of nuclear waste glasses during disposal in subsurface geological repositories. 5 , 9 , 18 , 24 In particular, natural and archeological glasses can be used to assess how the alteration layers on the glass may have formed in response to the near-field environmental conditions. Here, we characterize natural and archaeological glasses from five near-surface sites exposed to different environmental conditions (e.g., average temperatures, extent of hydraulic saturation, etc.). A detailed description of the sites is provided, along with characterization data for the excavated samples. The range of environmental conditions covered by these sites is relevant to the disposal of radioactive LAW glass at the near-surface, hydraulically unsaturated IDF at the Hanford site. DESCRIPTION OF SITES Integrated Disposal Facility (IDF) for low-activity waste (LAW) glass Unlike highly radioactive material, which will be buried deep underground in stable rock formations in a geological disposal facility, low activity radioactive waste does not require shielding and is suitable for disposal in shallower facilities closer to the surface. The Integrated Disposal Facility (IDF) is intended to be a near-surface disposal facility for radioactive LAW glass at the Hanford Site (Figs. 1 and 2 A). It is a large, lined disposal trench excavated ~ 13 m deep into the Hanford sands in the Central Plateau at the Hanford Site. The key engineered design features of the IDF consist of: (i) containers around the waste and a surface barrier placed above the waste limit water from contacting the waste; (ii) engineered backfill placed between and above waste containers to provide structural support after closure; (iii) borosilicate glass waste forms limit the release of contaminants due to the slow dissolution of the glass matrix. The key natural features consist of: (i) a semi-arid climate and shrub-steppe ecology that results in very little natural recharge to the groundwater due to low annual precipitation rates and high evapotranspiration; (ii) the thick vadose zone that delays the time it takes contaminants released from the source term to arrive at the saturated zone. The climate at the Hanford Site is mid-latitude semiarid desert. Daytime high temperatures in June, July, and August range from 17.2°C to 27.9°C but can exceed 40°C. During the winter, temperatures generally range from − 0.2°C to 6.9°C but can occasionally drop below − 18°C. The normal annual relative humidity is 54% and average annual precipitation is 17 cm. At the Hanford Site, basalt is underlain by Tertiary continental sedimentary rocks and overlain by late Tertiary and Quaternary fluvial and glacio-fluvial deposits. To establish limits on radionuclides that will be disposed of in the near-surface IDF, an assessment of impacts to groundwater resources must be made so that the concentration of radionuclides does not exceed the drinking water standard. To make this assessment, the alteration behavior of the LAW glass in the near surface environment of the IDF must be known. Analogue Site Similarities and Differences Samples were chosen from specific analogue sites to evaluate the following parameters: 1) how variation in surficial geology affects glass degradation; 2) effects of the environment on glass degradation; 3) comparison of sites with respect to the geology and current environment conditions, and possible environmental changes at the IDF; and 4) effect of hydraulic saturation (especially compared to the nominal conditions at the IDF). Several of these analogue glasses are from archeologically significant sites, therefore it was not possible to randomize sample collection, resulting in an unintentional bias towards sample types that were more widely available for characterization. The site characteristics, as detailed below, vary in terms of 1) the amount of time the glass was buried, 2) the chemical composition of the glass, 3) the surficial geology, 4) the environment (precipitation and climate), 5) burial depth, and 6) site elevation. Table 1 summarizes the analogue glasses chosen for study, Fig. 2 provides a map of the excavation sites, and Fig. 3 provides a timeline comparing relevant timescales (the alteration timescales for the analogue sites will be described in the subsequent sections). Information on the geologic setting for each site is available in the supplementary material. Table 1 Summary of glasses and alteration environments Site Type of Glass Origin and Age (y) Annual Precipitation (mm) Average Air Temperature (°C) Elevation Hanford, USA Borosilicate Wasteform for disposal of low activity radioactive waste, not yet produced ~ 170 ~ 12 IDF is 13 m deep, Hanford Site is 123 m above sea level Timna, Israel Melted granite, monzonite, monzodiorite, olivine norite, diorite, peridotite Copper slag, 1200–6000 30 − 15 ~ 21 ~ 300–450 m above sea level Broborg, Sweden Dark glass from melted amphibolite, clear glass from melted granite Rocks melted in box-like structures around a hillfort, 1,500 700 − 750 ~ 4.6 50 m above sea level/ near watershed Ballidon, UK Simulant Roman, Medieval, borosilicate, plate glass, soda lime, E-glass and lead optical Experiment to understand glass corrosion under alkaline conditions, 50 908 9.2 Buried in a model burial mound comprised of limestone fragments, 282 m above sea level Newberry, USA Obsidian, basalt, andesite, rhyolite, and pumice Last volcanic eruption: Big Obsidian Flow (BOF), ~ 1300–1400 ~ 900 0 On top of the BOF, 2433 m above sea level Dobkowice, Poland Soda-lime-silica glass Glass bead, 2600 700 mm 0°C Buried in grave ~ 1 m deep, 110 m above sea level Broborg Sweden Broborg (59°45’20” N, 17°57’06” E, elevation 49 m) Viking hillfort (Fig. 2 E) was established ~ 375–550 CE and used for approximately 175 years 18 in what is now the southeastern Uppland Province, ~ 25 km southeast of Uppsala. The technology and materials used to construct this hillfort are summarized by Sjöblom et al. 26 Vitrified rock samples were collected from the Broborg site during multiple excavations (1982-83, 1990 and 2017) described elsewhere. 27 , 28 Bulk sample analyses of the granite and amphibolite rocks were presented by Ogenhall. 29 Vitrified materials from the Broborg site were produced when the local amphibolite and granite were melted in situ . 26 , 30 – 32 The vitrification of the amphibole-rich rock produced a dark Fe and Mg-rich glass, while vitrification of the granite yielded a clear Na and Si-rich glass. The surficial layers observed on excavated samples were compared to surficial layers observed on excavated material that had been remelted to form coupons which, in turn, were subjected to laboratory testing (vapor hydration test, VHT, product consistency test, PCT, and EPA method 1313). 15 Broborg’s selection as an analogue site provided an opportunity to study ancient glass buried in a soil that is a mixture of ancient mountain soil and more recent till-derived sandy clay loam. 33 The overall climate of this site can be characterized as relatively humid and continental. Before the hillfort was constructed, temperatures were slightly warmer than the long-term average in the Roman Warm Period 34 (Fig. 3 ). When the fort was active, the Dark Age Cold Period (ca. 300–800 CE) was marked by temperatures below the long-term average. 34 Volcanism in Iceland caused temperatures to plummet from 536 to 539 CE. 35 36 The Medieval Warm Period saw an increase of 0.3 to 1.1°C compared to the local maximum. After the maximum, another cooling trend occurred during the Little Ice Age (LIA) before reversing around 1600 CE with warming to 2000 CE. 34 , 37 Timna, Israel Timna (Fig. 2 F), situated in the Aravah valley of the southern Negev desert (Israel), is known for its well-preserved historic copper mining districts that reveal at least 7000 years of archeological evidence of metallurgical activity. The region's tectonic and hydrothermal activities, combined with the specific rock types, contributed to the formation of copper deposits. 38 Ancient smelting sites provide evidence for copper production from the Copper Age to the Early Islamic Period. The vitrified slag samples from Timna described in the present paper were retrieved from copper smelting sites from the Early Bronze Age to the Early Islamic Age. 39 Timna's primarily hot desert climate and arid soils contrast starkly with those of the other analogue sites. The dominant soils in Timna are aridisols. 40 , 41 These are dry soils with limited organic matter and weak soil structure. Due to low rainfall and high evaporation rates, they are often saline. 40 , 42 , 43 Due to the limestone and chalk bedrock in regions around Timna, some soils exhibit a high calcium carbonate content, which can form hardpans or caliche layers. 44 Hyper-arid conditions have dominated the Aravah Valley 45 , 46 , due to it being located in the rain shadow of the Negev Highlands. 46 , 47 The middle Holocene experienced significant climate fluctuations, ranging from hyper-arid periods to intervals with higher levels of precipitation. 45 This was superseded by drier conditions with fewer oscillations in rainfall in the late Holocene. In the Middle Bronze Age to the end of the Late Bronze Age, humidity increased, followed by a sudden and pronounced ~ 150-year dry event occurring from 1300 to 1200 BCE. 45 The LIA was marked by increased aridity encompassing the Near East. 46 , 47 In the modern era, climate change has impacted Timna. The 20th and 21st centuries have seen a general trend of increasing temperatures, with precipitation patterns becoming more unpredictable and extreme. 48 Newberry, Oregon, USA Newberry Volcano, near Bend in central Oregon and east of the Cascade Range on the western edge of the High Lava Plains, is one of the largest and most active volcanoes in the contiguous United States. Samples were collected in 2021 from Newberry’s Big Obsidian Flow (BOF) (43°41’36” N, 121°13’45” W, elevation 2206 m) (Fig. 2 B). Newberry last erupted ~ 1,350 years ago (i.e., ~ 675 CE), resulting in the BOF. 49 – 52 The obsidian from the most recent flow contained 72.8 wt.% SiO 2 53 and differed from most other rhyolitic rocks on the Newberry volcano in their much higher Rb/Sr ratio. 50 Newberry samples were chosen for this study due to their natural origin, unique chemical composition, and differing climate. The soils that contact the BOF are andisols. They are primarily derived from volcanic materials and tend to have a loamy texture with a balance of sand, silt, and clay, thereby allowing good water infiltration and root penetration. 54 During the Medieval Climate Anomaly (MCA), the Newberry region experienced warmer and drier conditions. 55 During the LIA, cooler temperatures prevailed, with more frequent and extended wet periods influencing the region's ecosystems and human settlements. 56 Following the LIA, Newberry and Pacific Northwest regions' temperatures began to rise. The 20th and 21st centuries have seen an acceleration of this warming trend, consistent with global climate change patterns. Recent studies have shown a decline in snowpack levels in the Oregon Cascades and a trend toward earlier spring snowmelt. 50 , 53 , 57 Dobkowice, Poland Dobkowice is a town in Jarosław county of Poland’s Subcarpathian province, situated atop the northern edge of the Carpathian Foredeep geological basin. Approximately 30 glass beads and other artifacts from the Bronze age were excavated from a crematory gravesite (49°55'48.92" N 22°42'55.85" E, elevation 218 m) (Fig. 2 E) 58 . The glass beads were made using a mixture of natron and lime, or shells with sand. 59 Because of their soda-lime-silica composition, these glasses are commonly referred to as natron glass or low magnesium glass (LMG). The beads, relics of the Jordanów culture, are estimated to be ~ 2600 years old (i.e., ~ 430 ± 150 BCE) and vary in color from light green to light brown. 58 A local farmer discovered the site in 1971 a few hundred meters northwest of the town. Excavations were conducted in the 1970s and 1980s, and finally in 2011–2012 before construction of a highway began. 60 , 61 The Dobkowice site offers an opportunity to investigate anthropogenic glass buried in saturated soil in a relatively wet environment. The soil of the Dobkowice archeological site is an eutric fluvisol (soil base of saturation > 50%). 62 During the so-called Roman Warm Period (RWP) period (Fig. 3 ), Poland, along with the rest of Europe, likely experienced warmer climates, 63 with relatively colder and drier winters offset by warmer and wetter summers. 64 After the RWP, a cold period that lasted until about 800 CE brought cooler temperatures. During the last ~ 1000 years, until 1860 CE, summers and winters were colder than in previous millennia. 64 The Medieval Climatic Anomaly (MCA), or Medieval Warm Period, was characterized by a warmer phase with temperatures that may have resembled modern pre-industrial times (Fig. 3 ). 55 During the LIA, Poland and its surrounding areas experienced significantly colder winters and summers, which profoundly affected agriculture, settlements, and even warfare. 65 Post-LIA warming was observed in Dobkowice and the surrounding region. In the 20th century, warming accelerated due to anthropogenic factors. 66 In recent decades, Poland has experienced higher temperatures, changes in precipitation, and increased extreme weather events such as heat waves and heavy rains, with an overall trend of rapid warming. 67 Ballidon, UK The Ballidon quarry site offers a controlled environment allowing the study of both natural and anthropogenic glasses. The Ballidon glass burial experiment (53°05’38’N, 1°42’08” W, elevation 228 m) (Fig. 2 C) was initiated in 1963, based on preliminary results from buried glass samples from the Experimental Earthworks in Wareham. 68 Various glasses were buried, including replica Roman soda–lime–silica glass, potash–lime–silica circa 17th century, and medieval glass. 69 The pore water pH conditions at Wareham were acidic, so the degradation of the glass samples was slow. In order to speed up the corrosion process and thus produce measurable effects over the short term, it was decided to bury an identical selection of glass samples in an alkaline environment (i.e., glasses buried in a limestone quarry). 68 , 70 . Samples at Ballidon were placed in a burial site originally measuring 3.5 m ×1.5 m and covered in limestone fragments, comprising of pieces of crushed limestone (1 cm − 8 cm fragments of calcite). 71 At a sample depth of < 20 cm, samples may occasionally have been affected by severe frosts. The soils at the Ballidon are loamy brown peaty topsoils underlain by clay subsoils, with an average pore water pH of 9.6. 72 , 73 Over the past 50 years, Derbyshire's climate has become slightly warmer and wetter, paralleling broader climatic trends across the UK. 71 According to the UK Meteorological Office, the average temperature in the UK increased around 0.8°C between 1961–1990 and 1991-2020. 71 This increase was most substantial in central and eastern England, where some areas saw temperatures rise by more than 1.0°C. 71 Despite elevated precipitation conditions, there are intermittent drying periods during the summer months. These fluctuating environmental conditions, as compared to other disposal sites, may be responsible for their unique alteration signatures. 74 The experiment was planned to run for 512 years, with the extraction of samples from sites within the mound at increasingly-spaced time intervals: 1, 2, 4, 8, 16, 32, 64, 128, 256 and 512 years. 68 The 64-year sample retrieval was brought forward in time due to interest in nuclear waste-form glasses. From 1986 onwards, simulant nuclear waste glasses, including glass formulations from the UK, USA, and Russia, have been buried in vacant sites at Ballidon for various periods of time. Similar glass burial experiments have also been undertaken elsewhere, including Chalk River Nuclear Laboratories (CRNL) in Ontario, Canada (1959–1978), 75 the Stripa granite mine, Sweden (1982), 76 the Boom clay in Mol, Belgium (1986), 76 the halite disposal facility at the waste isolation pilot plant (WIPP) at Carlsbad, New Mexico (1986), 77 and the Hanford lysimeter site (present day) in glacial lake deposits and gravel. 78 To directly compare the effects of local environmental factors on glass alteration, the same simulant nuclear waste glasses have been buried at the Stripa, Mol, Ballidon, Carlsbad, and Hanford sites. 76 A discussion of other near-surface burial sites is provided elsewhere. 79 RESULTS Analyses were performed on analogue samples from the five sites, and results are discussed in terms of the chemistry of the analog glasses, followed by observations and measurements of the surficial alteration layers prepared in cross section (or in some cases, ‘as-is’). Table 2 provides measured bulk compositions for samples from the five sites. These bulk compositions were measured using either EPMA or ICP-OES and ICP-MS following chemical digestion. Table 2 Comparison of select site sample compositions Component MJS1 BB1b (Na/Si-enriched) BB1b (Mg/Fe-enriched) Dobkowice Replica medieval glass (Hangleton) Timna tuyère Site 28 (representative of Timna samples A-G) Site 201 (Timna sample H) Site 34 (Timna samples I-K) Location Newberry Broborg Dobkowice Ballidon 86 Timna SiO 2 70.14 64.26 53.86 75.08 46.5 60.88 55.89 77.76 56.45 Al 2 O 3 13.93 15.82 12.77 0.36 3.5 19.60 0.89 8.78 1.03 Na 2 O 4.76 3.70 2.78 17.76 0.7 0.57 0.44 0.47 0.55 Fe 2 O 3 3.48 5.25 12.83 0.17 1.2 11.04 21.5 6.4 22.76 CaO 0.88 3.33 8.73 7.29 21.6 2.21 5.07 1.19 1.53 K 2 O 4.04 4.81 1.39 0.11 16.4 1.63 0.92 1.14 1.25 MgO 0.22 1.97 6.68 0.36 5.4 0.70 0.79 0.26 0.38 MnO 0 0.10 0.43 0 0 0.02 1.71 0.01 4.73 P 2 O 5 0 0.58 0.20 0.06 4.6 0.18 0.67 0.08 1.88 TiO 2 0.22 1.04 0.89 0 0 0.91 0.2 1.78 0.31 ZrO 2 0.08 0 0 0 0 0 0.06 0.04 0.11 CuO 0 0 0 0 0 0.05 5.03 0.16 1.98 BaO 0 0 0 0 0 0 0.09 0.01 0.33 Cr 2 O 3 0 0 0 0 0 0 0.03 0.01 0.02 Cl 0 0 0 1.01 0 0 0 0 0 Others 0 0 0 0.32 0 0 6.71 1.91 6.69 Total 97.74 100.87 100.38 102.53 99.9 97.786 100 100 100 Method EPMA Chemical digestion, ICP-OES, ICP-MS Timna For the samples that were excavated from Timna, the twelve samples chosen for analysis were biased toward material with high glass contents. These twelve analogues include eleven glassy slag samples and one tuyère sample that were taken from three smelting sites in or near the Timna Valley: site 28, site 34, and site 201. The tuyère sample (Site 34) is approximately 3150 years old. 87 The tuyère was a ceramic nozzle forming part of the bellows that were placed inside the furnace, usually pointing down to direct a forced draught towards the lower charcoals. The tuyère withstood extreme heat inside the furnace, with the area around reaching temperatures of approximately 1300–1500°C, allowing for molten metallurgical slag to accumulate on the tuyère, which mostly vitrified on cooling. 88 Site 28, named the Be’er Ora “Slag Valley”, was a big smelting camp located south of Timna Valley. Radiocarbon dating of samples from site 28 found that these materials mostly dated to the 7th -10th centuries CE. 89 – 91 Site 34, named “Slaves Hill”, has been the central site of the Central Timna Valley (CTV) project that has been led by Tel Aviv University. It was excavated between 2012 and 2023 and has received the most attention of all Timna sites. Radiocarbon dating revealed that smelting occurred roughly between the late 11th and 10th centuries BCE. 87 Site 201 is located on top of a small hill on the western side of the Aravah, just 5 km north of Timna Valley. The CTV Project excavated Site 201 in 2020 to further understand technological developments associated with the very early history of extractive metallurgy. Radiocarbon dating suggests that the site was active at several periods, from the end of the late Copper (4000 BCE) to the Early Bronze Age. Table 3 compares the amorphous contents of twelve Timna samples determined by XCT and XRD (using semi-quantitative Rietveld refinement) and lists the approximate ages of the samples. Figures 4 and 5 show XCT reconstructions and optical micrographs of eleven Timna samples, while Fig. 6 shows the corresponding XRD patterns. Overall, the more recent samples exhibit larger amorphous contents, which is attributed to improvement in the melting technology with time leading to faster heating and cooling rates in the furnace. All the Timna samples show a thin surficial coating. The surficial layer on the tuyère sample, which is the sample containing the highest glass content, is not visible along the entire surface, but has a consistent thickness in the regions where it is observed. Figure 7 shows a ~ 2 µm thick surficial layer on a Timna sample obtained using SEM. The back scattered electron (BSE) image shows heterogeneities in mass-density within the layer, which is particularly noticeable when compared to the uniform unaltered bulk material. Silicon shows no major change in concentration, whereas Mg is enriched in the layer. The interfacial gradient in the Mg concentration, at the scale of the image, is relatively sharp. The bulk region does show a few white circular regions, whose origin is not known. It is interesting that these circular areas are enriched in Cu and depleted in Si. There is also a very thin dark band of material (i.e., elevated mass-density) at the inner boundary between the surficial layer and the bulk. Both the inner and outer interfaces of the dark band are very sharp. Figure 8 shows the same area measured by ToF-SIMS. The elemental maps show that the surficial layer has a constant thickness (~ 2–3 µm) and is enriched in H, Mg, Al, Si, K, and Cu (Cu just slightly), and depleted in Na and Ca. All enriched elemental maps (including Ca) display some heterogeneity, characterized by small, localized areas with higher-than-average concentrations. The surficial layer has an additional and extremely thin but non-continuous external layer that shows even higher enrichment in Mg, Al, Si, and K. This very thin layer is also evident in the SEM-BSE image of Fig. 8 . Both the chemical maps and the BSE image show the same thin band at the inner boundary that separates the surficial layer from the bulk (Fig. 7 ). This black band may point to a physical gap, suggesting that the layer is not strongly bound to the bulk material. Table 3 Comparison of amorphous contents (measured by XCT and XRD) and sample ages for twelve Timna samples Sample XCT solid inclusions volume fraction XCT Amorphous volume fraction XRD amorphous mass fraction Approximate Sample age (years) Sample Location Timna-A 3.1% 96.9% 91.1% 1200 ± 150 Site 28 Timna-B 0.1% 99.9% 92.8% 1200 ± 150 Timna-C 0.1% 99.9% 97.7% 1200 ± 150 Timna-D 0.1% 99.9% 99.3% 1200 ± 150 Timna-E 0.1% 99.9% 90.8% 1200 ± 150 Timna-F 0.1% 99.9% 89.8% 1200 ± 150 Timna-G 0.1% 99.9% 97.8% 1200 ± 150 Timna-H* > 90% BQL 21.7% 3100 ± 100 Site 34 Tuyère N/A N/A N/A N/A Timna-I > 90% BQL 12.8% 4500 ± 200 Site 201 Timna-J > 90% BQL 8.3% 4500 ± 200 Timna-K > 90% BQL 23.0% 4500 ± 200 BQL = below quantitative limit *indicates sample matrix appeared homogeneous by XCT but featured crystalline phases of size smaller than the minimum voxel size Ballidon Results are presented for a replica medieval glass sample (of potassium-lime-silica composition, designed to replicate a specific glass known as the “Hangleton linen smoother” 86 ) excavated from the Ballidon experimental mound. 74 This sample was altered under near-surface conditions for a duration of 52 years before retrieval. The sample was mounted in epoxy and analyzed using EPMA. Figure 9 shows SEM-BSE images and elemental maps of the altered surface layer (SL) of the replica medieval glass sample. After 52 years, the alteration layer on this sample is considerably thicker than those on the Timna samples, ranging from 400 µm to 1000 µm. The SL is not homogeneous but appears to change abruptly in the sub-layer adjacent to the soil, with respect to the presence of gaps or pores between the much thinner layers. The elemental distributions of the various elements show an alternating pattern of bands corresponding to element depletion and enrichment. The SL, furthest from the pristine glass, appears more chemically separated (‘banded’) whilst the younger alteration next to the pristine glass appears more uniform. The bands of enrichment and depletion also appear to be anti-correlated. Using the fiducial (red line) shown in panel B as a guide, the bands enriched in Al, Si, and possibly K are spatially correlated with the same bands showing depletion in Ca, P, Fe, and Mg (panel C). The chemical boundaries of the bands are relatively sharp, except for Na and K, which are in part indistinct. The band widths vary in thickness (10–25 µm), which is particularly evident in the Fe, Si, P, and Ca maps. Such banding was also present in the Roman glass from the Iulia Felix shipwreck. 20 , 92 , 93 Dobkowice An SEM-BSE image of a polished section of a glass bead from the Dobkowice burial site is shown in Fig. 10 A. Surficial alteration of this sample takes the form of a distinct thin rim surrounding the entire sample. The rim appears to exhibit spalling, which is most likely an artefact created during sample embedding in epoxy. The actual boundary of the spalling is not strictly correlated to the boundary of the alteration rim with the bulk glass. The high-resolution SEM-BSE image in Fig. 10 B shows that the rim is composed of a relatively homogenous ~ 50 µm-thick surficial layer (SL#1) with a sharp interface with the bulk glass interface. There is also a very thin and heterogenous over-layer (SL#2) that represents the topmost part of the alteration rim, and these two layers resemble those in Fig. 8 . The SEM-EDX map in Fig. 10 C shows that the surficial layer can vary in thickness, here it is on the order of 50–100 µm. The principal alteration layer (SL#1) is depleted in Na and enriched in Si and Al. Figure S1 shows SEM-EDS maps overlaid on SEM-BSE images from a non-polished ‘as-is’ fractured surface from the Dobkowice sample, confirming that SL#1, the layer that is Na-poor and Si and Al-rich is attached to the bulk glass, and that the spalling in Fig. 10 is due to sample preparation. The principal alteration layer shown in Fig. 10 C displays a more complex morphology, as evidenced, for example, by the Al-rich vesicle. It is unclear if the Al-rich vesicle is a result of a glass alteration process, or if it is soil that was incorporated into the surficial layer. This vesicle bears an uncanny resemblance to vesicles seen in oceanic basalt glasses that have been ascribed as being due to microbially-enhanced dissolution. 81 The SEM-BSE image in Fig. 11 reveals a dominant alteration layer (SL#1) with a uniform thickness of approximately 30 µm. There is very little mass-density difference between SL#1 and the bulk glass. The large crack is an epoxy-embedding artefact and should not be confused with the SL#1 interface with the bulk glass. The ToF-SIMS chemical maps in Fig. 11 chemical maps illustrate that the principal layer (SL#1) is hydrated (as shown in the H + map), enriched in Si, Ca, and just slightly in Mg, and depleted in Na, K, and Al. The principal alteration layer has a very thin external rim (SL#2) characterized by strong Al and K enrichment. Broborg Sample BB1b was originally excavated from the Broborg hillfort, as described in the literature. 15 , 30 , 94 , 95 It was selected for study because it has a significant fraction of glassy material and the surface appeared altered through natural processes. 94 , 96 Fig. 12 shows an optical microscopy image and SEM-EDS elemental maps of the sample prepared in cross-section. In Fig. 12 , the term ‘bulk’ refers to a glassy phase that was created during melting of the protolith rocks and ‘SL’ refers to the surficial layer. The surface of the bulk glass is predominantly mafic, as the mafic glass is two orders of magnitude less viscous than the felsic glass and flowed over the felsic material. 96 Compared to the bulk mafic glass, the surficial layer shown in Fig. 12 B is enriched in Si and depleted in Na, Al, Mg, Ca, and Fe. The surficial layer in Fig. 12 C, is also depleted in Na and Fe, and enriched in Si. Ca is depleted, except for certain hotspots with elevated concentrations. The behavior of Mg and Al in the surficial layer is more complex with areas of both enrichment and depletion. The textural and chemical heterogeneity of the bulk glass makes the evaluation of surficial layer formation challenging in samples from the Broborg hillfort. SEM-EDS maps of a larger area of the Broborg BB1b sample are shown in Fig. 13 , highlighting the surficial layers associated with the mafic region (individual maps shown in Fig. S2). The alteration layer is highly irregular in morphology and has an approximate average thickness of 14 µm. The chemical composition of the altered layer differs from the amorphous matrix: Si is enriched, Al is depleted, and Fe, Mg, and Na are completely absent, having concentrations below the detection limit (see individual SEM-EDS elemental maps in Fig. S2). Figure 13 shows the textural and chemical heterogeneity of the bulk glass, with felspar needles, and irregularly shaped iron-bearing pyroxenes and spinels (identified by X-ray diffraction in Matthews et al. 94 ) that are present throughout the glassy matrix. These crystalline phases are also present at the interface to such an extent that the glass matrix is rarely in contact with the surficial layer. The aqueous alteration rates of crystalline silicates and spinels are predicted to be significantly slower than silicate glasses. It is uncertain whether alteration of the glass proceeded until the alteration front reached a crystallite, or if these phases crystallized near the surface of the original bulk glass. However, it can be hypothesized that the composition and structure of the underlying matrix had a direct impact on the surficial altered layer. Newberry Results are presented for three samples (MJS-1, BOF-6, and BOF-9) from the Newberry volcano Big Obsidian Flow. Samples BOF-6 and BOF-9 were both excavated in the same approximate vicinity; however, BOF-6 was partially covered in soil while the BOF-9 sample was excavated from one of the walls of the obsidian flow. Sample MJS-1 was taken from the top of the flow. Figure 14 shows optical and SEM-BSE images of obsidian samples, including photographs taken from near the excavation sites of the three Newberry samples. Visually, the surfaces of MJS-1 and BOF-6 (Figs. 14 A, E, respectively) both appeared white while the surface layer of BOF-9 had a reddish tint (Fig. 14 C). However, the BOF-6 surface layer was much more friable, while the surface layer of MJS-1 was consolidated. Both the MJS-1 and BOF-6 samples contained evidence of plant roots present on their surfaces. The SEM-EDS elemental maps of sample MJS-1, in Fig. 14 B, show a relatively non-porous surficial layer that has a variable thickness, ranging from a few µm to ~ 20 µm. In general, this surficial layer was visible along the sample surface that was exposed to the atmosphere. The SEM-EDS chemical map of the BOF-9 sample in Fig. 14 D shows that the red-colored surficial layer is composed of a highly porous, sponge-like structure that is compositionally similar to the underlying obsidian glass, with a minor fraction of particles, either Fe or Na-rich. The SEM-EDS chemical map of the BOF-6 sample, shown in Fig. 14 F, reveals a smooth surface that is amply covered with silicon-rich features that are most likely diatoms. 81 At the scale of this image, there is no obvious evidence of an altered layer. Figure 15 shows ToF-SIMS ion maps of the altered layer of sample MJS-1. The maps show a ~ 10 µm-thick surficial layer with sharp chemical boundaries at both the inner and outer interfaces. The altered layer appears to be very heterogeneous with respect to its structure and composition, as shown in the SEM-BSE image (Fig. 15 ). This heterogeneity is also reflected in the chemical maps. Na and K are depleted in this layer, while H, Mg, Al, Si, Ca, and Fe are enriched. The depleted and enriched layers are spatially coincident for all elements. The one exception is H, as this element displays two zones: (i) a prominent outer zone of elevated H enrichment is ~ 10 µm thick; and (ii) an adjacent, inner zone ~ 4 µm thick that is characterized by H concentrations just barely above that of the bulk obsidian. Both H zones have relatively sharp boundaries at the scale of the analyses. This contrasts with the H map of the Timna sample (Fig. 8 ), which showed only one very sharp layer of H enrichment. DISCUSSION AND CONCLUSIONS The natural and archeological analogues presented here were exposed to different environments for different lengths of time. The analogues were of different chemistry, a parameter that is intimately tied to technological developments, including the ability to melt materials at increasingly higher temperature due to improvements in the high-temperature processing technologies that were employed and the chemistry of the primary material sources used (important for controlling such factors as chemical impurities and oxidation state 97 ). The factors of environment, length of time, and chemical composition of the starting material had an influence on the chemistry and morphology of the surface layers and secondary phases that developed in contact with the unaltered bulk glasses. These factors are summarized along with average surficial layer thicknesses in Table 4 . The use of surficial altered layer thicknesses to compare and estimate rates of glass corrosion should be viewed as very approximate for many reasons. One reason is molar volume changes between the unaltered glass and the phase(s) making up the altered layer. Moreover, the effects of porosity in the altered layer also must be considered. It also cannot be excluded that over time during burial and then retrieval from the soil, some of the surface altered layers may have lost their structural integrity, causing secondary phases to peel or break off, thereby making the altered layers incomplete and thinner. The archeological samples described in this study were excavated from near-surface conditions in hydraulically unsaturated environments. This is important as they can be used to support the disposal of LAW glass at the Hanford site IDF. The nominal conditions at the Hanford IDF are an average subterranean temperature of 15°C at a 7.6-m depth with an annual rainfall of 180 mm. 98 After the waste and associated backfill have been placed in the facility, it will be covered with an engineered surface barrier. An infiltration rate of 0.5 mm/year is assumed while this barrier is intact, with the infiltration rate increasing to 3.5 mm/year once the barrier has degraded (after ~ 500 years). 98 Water infiltrating through the backfill will chemically react with the dominant minerals present, which are mostly comprised of silica, as well as some carbonates. The carbonates minerals will lead to buffering of the pore waste to neutral-to-mildly alkaline pH conditions. The IDF temperatures and annual rainfall quantities are closer to those of Timna than the other analogue sites. The glass compositions expected at the IDF are different from the glasses from the analogue sites, having lower Si, Fe, and Al, higher Na, as well as components that are not present in the analogues, including B, Li, V, and Sn. The Ballidon site and other field-testing sites will provide important data on the alteration of compositionally relevant borosilicate glasses in near-surface conditions relevant to the Hanford IDF. Analysis of alteration observed on archeological and modern glasses (including one borosilicate composition) buried at the Ballidon site for 52 years is described in Thorpe et al. 74 Furthermore, analysis of US and UK nuclear waste type glasses buried for 18 and 20 years, respectively, is underway and includes borosilicate, silicate, and Fe-phosphate compositions. An additional test with buried LAW glass samples has also been underway since 2019 and data from those tests will inform glass behavior in the IDF, 79 even though the duration of those tests is much less than that achievable with the archeological glass samples. The present work characterizes the surficial alteration features of natural and archeological glasses as a function of the burial environment and the bulk glass composition. The characterizations that were performed confirmed that the samples contained a significant fraction of glassy material. These glassy materials were subjected to alteration under near-surface conditions for periods exceeding 1000 years and fulfil the criteria to be considered as an alteration analogue, since they 3 , 5 , 25 : (i ) are of a known or determinable chemistry (e.g., composition and structure); (ii) are from a known or determinable alteration environment (e.g., exposure time, biological contact, solution chemistry, etc.); (iii) are of a known or determinable provenance following its excavation (e.g., storage conditions, sampling history, conservation/restoration, etc.); and (iv) are measurably altered. The physico-chemical characterizations revealed that differences in the chemical composition of the original samples significantly affected their chemical durability. The data in Table 4 suggest that the average annual air temperature and annual precipitation also have a measurable effect on the observed thickness of the altered surficial layer. Due to the nature of the analogues and their environments (lack of duplicates, different compositions, different temperatures, different rainfall, etc.), it is challenging to isolate the parameter that has a largest effect on surficial layer thickness, and further characterization of samples from additional sites is needed in the future. However, the data show that samples altered in the arid Timna environment have thinner surface layers than samples subjected to greater annual precipitation levels. It is important to note that air temperature and average precipitation do not fully parameterize the exposure conditions for these samples, and that future work will investigate the influence of the soil pore water chemistry and the local microbial community on glass alteration. During efforts to characterize and assess the Broborg glasses as alteration analogues, evidence of microbial interaction with the glass surfaces was observed via SEM. 18 Further microscopic and spectroscopic analyses showed glass alteration (chemical and morphological) consistent with microbial activity, evidenced by surficial pitting beneath microbes, suggesting a microbial component to glass corrosion. 99 Bacterial and fungal communities can colonize a variety of natural and synthetic materials, including rock and glass, by forming complex biofilms on the surfaces. 27 These microbial biofilms are known to weather these material surfaces using biophysical and biochemical processes (such as penetrating within cracks, producing extracellular polysaccharides, and secreting organic acids). 100 Decades of research have established that microbial communities can persist and even thrive in harsh and toxic environments, suggesting the potential for biotic processes to influence the alteration of vitrified low-level nuclear waste after storage in near-surface geological facilities. 27 , 99 , 101 , 102 However, most studies evaluating the long-term durability of vitrified nuclear waste glass have focused on the abiotic degradation of these materials in sterile environments. 100 While the presence of microbes in these geological facilities is recognized, 103 , 104 only a few studies have attempted to characterize and extrapolate the observed short-term microbial impacts to predict the long-term (i.e., thousands of years) bio-alteration of vitrified nuclear waste, and this is an ongoing area of research. 27 , 100 , 105 , 106 To conclude, the knowledge obtained on how different environmental factors influence the alteration of vitrified archeological samples can be applied to vitrified nuclear waste materials. The subsequent incorporation of these factors into performance assessment models will allow for the development a more holistic long-term prediction of the vitrified material durability under field conditions. Table 4 Summary of analogue glass site data Site and sample Average SEM surficial layer thickness, µm Average air temperature and annual precipitation Sample age Description of chemical and mineralogical makeup Analogue Advantages Analogue Limitations Timna Tuyère 2 ± 0.2 15°C, 25 mm annual rainfall. Arid with periodic floods 46 3150 ± 50 yrs Copper slag (iron-rich glass with fayalite and copper-rich inclusions) Various alteration timescales, arid, amorphous, known provenance, near surface Open system, heterogeneous, more arid than IDF, limited alteration Broborg-BB1b 8 ± 2 (felsic glass), 13 ± 10 (mafic glass) 5°C, 572 mm annual rainfall 94 1500 yrs Either mafic-derived glass + spinel + pyroxene or felsic-derived glass + quartz + feldspar Difference glass chemistries, known provenance, near surface Heterogeneous, challenging surface analyses, more rain than IDF Ballidon Variable depending on sample (> 400 µm for replica medieval glass) 9–10°C, 908 mm annual rainfall 107 18–52 yrs Silicate, borosilicate, lead-silicate and Fe-phosphate compositions (US, UK and Russian nuclear waste glass) Different glass chemistries, controlled experiment, high rainfall, near surface Short alteration timescale, cooler and more rain than IDF Newberry-MJS-1 8.65 ± 5.24 0°C, 635 mm annual rainfall 108 , 109 1350 yrs (most recent lava flow) Obsidian Homogeneous, natural, known provenance Not buried, only one glass chemistry Dobkowice 59 ± 2 0°C, 700 mm annual rainfall 110 2600 yrs Soda-lime-silica glass Various alteration timescales, arid, amorphous, known provenance, near surface Open system, heterogeneous, more arid than IDF, limited alteration METHODS One of the main goals of the present study is to provide a general physical and chemical characterization of glass analogs recovered from the five sites. The techniques used provide information at various scales, with a maximum of micrometer-spatial resolution. Future work will involve techniques that have much higher spatial and mass resolution, such as transmission electron microscopy (TEM), atom probe tomography (APT), TEM-tomography, nano secondary ion mass spectrometry (nanoSIMS), etc. to characterize the altered samples. Such high-resolution analysis techniques have been shown to provide significant insights into the interfacial region that delimit the boundary between the non-altered parent material and overlying authigenic surface layers (SL). Atomic scale measurements are crucial for future interpretation of the mechanisms of alteration. 80 – 83 Optical microscopy, scanning electron microscopy (SEM), and electron probe microanalysis (EPMA) Optical microscopy was performed with a Keyence VHX 7000 optical microscope. Samples were observed either ‘as received’, to evaluate surficial layers prior to any additional sample preparation involving exposure to water, or as polished sections for more detailed characterization of the chemistry and morphology. Polished sections were made by first fracturing bulk material, embedding grains in epoxy, and then polishing sequentially with 240, 320, 400, 600, 800, and 1200 grit SiC abrasive paper in the presence of water (exposure to water during polishing is on the order of minutes compared to the hundreds of years the archeological samples have been in contact with water and should have a negligible impact on alteration layer thickness and morphology). This was followed by polishing with a 1-µm diamond paste suspension. Much higher spatial resolution imaging of polished sections was performed using a JEOL 7001F SEM operated with a 15 kV accelerating voltage and 13 nA probe current. Energy-dispersive spectroscopy (EDS) analyses were performed with a Bruker Xflash 6 60 X-ray detector with a spectral resolution of 129 eV. Energy-dispersive X-ray spectra were processed using Bruker Esprit v2.1 software. Higher accuracy chemical composition measurements were made by electron probe microanalysis (EPMA) using a JEOL 8530 instrument operated with a 15 kV accelerating voltage and 20 nA probe current. Wavelength-dispersive spectroscopic (WDS) measurements were made with five spectrometers for high-energy resolution compositional measurements and analysis of light elements. X-ray computed tomography The internal 3-D microstructure of the samples was analyzed using X-ray micro computed tomography (micro-CT) using a Thermo Fisher Scientific Heliscan Micro-CT system. Samples were mounted on Styrofoam and scanned with an 80 kV p unfiltered microfocus X-ray source with a < 1.5 µm diameter focal spot. Projections were acquired in a space-filling trajectory with a detector shift applied to help lessen the impact of pixel-specific artifacts. The acquired projections were reconstructed on a GPU cluster using iterative methods, yielding digital 3D volumes with voxel sizes around 5 µm 3 . Image segmentation was performed on the X-ray projections to partition the projections into: (i) bulk phase of the samples (assumed to be the amorphous phase); (ii) bright inclusions (assumed to be crystals); (iii) voids; and (iv) background. The segmented projects were then stitched together to form a reconstructed 3-dimensional representation of the samples and the voxels corresponding to the amorphous phase were summed and normalized to the total volume of the amorphous and crystalline phases. X-ray diffraction (XRD) XRD was performed with a Bruker Advance D8 X-ray diffractometer using a Cu K α X-ray source operated at 40 kV and 40 mA. Samples were either in bulk form or fine powders that were produced using a tungsten carbide mill. For semi-quantitative amorphous fraction analysis, sample powders were mixed with a 5 wt.% CeO 2 internal standard. XRD scans were collected from 5–70° 2θ with a step size of 0.015° and a dwell time of 30 s. Phase identification of XRD patterns was carried out with EVA 4.0 using the PDF4 + database from the Inorganic Crystal Structure Database (ICSD). Rietveld refinement was used for semi-quantitative analyses of the amorphous sample fractions with TOPAS 4.0 software. Time of flight secondary ion mass spectroscopy (ToF-SIMS) ToF-SIMS measurements were performed using a ToF.SIMS5 instrument (IONTOF GmbH, Münster, Germany). ToF-SIMS has many advantages of SEM-EDS, including improved elemental detection limits and the ability to measure hydrogen (H). The distribution of H in the alteration layer of polished analogue samples was measured using experimental conditions optimized for high signal-to-noise (S/N) ratios of H. 84 A 25.0 keV Bi + beam was used as the analysis beam to collect positive secondary ion maps of the following ions: H + , Li + , Na + , Ca ++ , Ca + , Si + , 30 Si + , Al + , Mg + , C + , K + , Cu + , and 54 Fe + . A 1.0 keV O 2 + sputter beam with 240 nA current was used before and during analysis to remove surface contamination and control the hydrogen background. The O 2 + beam was scanned over a 700×700 µm 2 area for 600 s before data collection to remove surface contamination. During collection of ion maps, the instrument was operated in a non-interlaced mode. The Bi + beam was focused to a 400 nm diameter with a beam current of 1.70 pA at 20 kHz frequency. Maps were acquired over 200×200 µm 2 , 150×150 µm 2 , or 50×50 µm 2 areas with 256×256 pixels. During non-interlaced mode imaging collection, each cycle was composed of three steps: (i) the O 2 + beam was scanned over the sample for 1 s to remove H adsorbed on the surface to control the H background, (ii) a 0.5 s pulse was used for charging control so that reasonable signal intensity could be achieved, (iii) 2 scans for ion map collection, with 256×256 pixels per scan. 50–200 scan cycles were accumulated during data collection. Chemical digestion and elemental analysis Chemical digestion was carried out by microwave assisted acid digestion. Inductively coupled plasma-optical emission spectroscopy (ICP-OES) analysis was performed on an Agilent 5110 VDV (Agilent Technologies, Santa Clara, CA) for major elements. Inductively coupled plasma-mass spectrometry (ICP-MS) was performed with a Perkin Elmer model NexION 2000B for trace elements (i.e., Cr and Zr). The chemical digestion procedure and subsequent elemental analyses were performed following test protocol USEPA3052B. 85 Declarations Author Contribution J.M., J.C., J.N., C.P., R.G., R.H., C.T., E.B., J.M., D.K., R.H., R.S., and A.K. wrote main manuscript text. Z.Z. performed ToF-SIMS measurements. A.D. and S.L. performed XCT measurements. L.B., E.G., O.Y., E.B., and D.K. provided Timna samples and wrote sections related to Timna. R.H. and C.T. provided data for Ballidon and wrote Ballidon section. R.G., J.C., P.N., and M.S., provided Dobkowice samples. M.J. provided Newberry samples and project guidance. S.C., J.H., A.P., N.B., R.A., and A.K. performed laboratory measurements. All authors reviewed the manuscript Acknowledgement This work is supported by the Waste Treatment and Immobilization Plant Project at the United States Department of Energy (US DOE) Hanford Field Office (HFO). The authors gratefully acknowledge Professor Peter Kresten for supplying the original vitrified samples from Broborg and Professor Sylwester Czopek for help with archeologic data of the Dobkowice sample. A portion of the research was performed using the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research located at Pacific Northwest National Laboratory under proposal number 60748 (Award DOI: 10.46936/lsr.proj.2023.60748/60008973). Pacific Northwest National Laboratory is operated for the DOE by Battelle Memorial Institute under Contract DE-AC06–76RLO 1830. Data Availability Data sets generated during the current study are available from the corresponding author on reasonable request. References Crovisier, J.-L., Advocat, T. & Dussossoy, J.-L. Nature and role of natural alteration gels formed on the surface of ancient volcanic glasses (Natural analogs of waste containment glasses). Journal of Nuclear Materials 321, 91–109, (2003). Techer, I. et al. Alteration of a basaltic glass in an argillaceous medium: The Salagou dike of the Lodève Permian Basin (France). Analogy with an underground nuclear waste repository. Geochimica et Cosmochimica Acta 65, 1071–1086, (2001). Miller, W. et al. Natural Analogue Studies in the Geological Disposal of Radioactive Wastes. Report No. DOE-HMIP-RR–94031, (United Kingdom, 1994). Lutze, W. et al. Alteration of basalt glasses: implications for modelling the long-term stability of nuclear waste glasses. Nature 314, 252–255, (1985). Ewing, R. C. Natural glasses: analogues for radioactive waste forms. Materials Research Society Symposium Proceedings 1, 57–68, (1979). Techer, I., Advocat, T., Lancelot, J. & Liotard, J. M. Basaltic glass: alteration mechanisms and analogy with nuclear waste glasses. Journal of Nuclear Materials 282, 40–46, (2000). Malow, G. & Lutze, W. Alteration Effects and Leach Rates of Basaltic Glasses: Implications for the Long-Term Stability of Nuclear Waste Form Borosilcate Glasses. Journal of Non-Crystalline Solids 67, 305–321, (1984). Libourel, G. The use of natural and archeological analogues for understanding the long-term behavior of nuclear glasses. Comptes Rendus Geosci. 343, (2011). Ewing, R. C. & Roed, G. Natural analogues: Their application to the prediction of the long-term behavior of nuclear waste glasses. Materials Research Society Symposium Proceedings 84, 67–83, (1987). Michelin, A. et al. Effect of iron metal and siderite on the durability of simulated archeological glassy material. Corrosion Science 76, 403–414, (2013). Ryan, J. et al. Ancient Roman Glass Characterization for use in Glass Corrosion Modeling. Report No. PNNL-21847, (Pacific Northwest National Laboratory, Richland, WA, USA, 2012). Verney-Carron, A., Gin, S. & Libourel, G. A fractured roman glass block altered for 1800 years in seawater: Analogy with nuclear waste glass in a deep geological repository. Geochimica et Cosmochimica Acta 72, 5372–5385, (2008). Verney-Carron, A., Gin, S., Frugier, P. & Libourel, G. Long-term modeling of alteration-transport coupling: Application to a fractured Roman glass. Geochimica Et Cosmochimica Acta 74, 2291–2315, (2010). Verney-Carron, A., Gin, S. & Libourel, G. Archaeological analogs and the future of nuclear waste glass. Journal of Nuclear Materials 406, 365–370, (2010). Nava-Farias, L. et al. Applying laboratory methods for durability assessment of vitrified material to archaeological samples. npj Materials Degradation 5, 57, (2021). Techer, I., Advocat, T., Lancelot, J. & Liotard, J. M. Dissolution kinetics of basaltic glasses: control by solution chemistry and protective effect of the alteration film. Chemical Geology 176, 235–263, (2001). Zanini, R., Franceschin, G., Cattaruzza, E. & Traviglia, A. A review of glass corrosion: the unique contribution of studying ancient glass to validate glass alteration models. npj Materials Degradation 7, 38, (2023). Weaver, J. L. et al. Pre-viking Swedish hillfort glass: A prospective long-term alteration analogue for vitrified nuclear waste. International Journal of Applied Glass Science 9, 540–554, (2018). Silvestri, A. The coloured glass of Iulia Felix. Journal of Archaeological Science 35, 1489–1501, (2008). Silvestri, A., Molin, G. & Salviulo, G. The colourless glass of Iulia Felix. Journal of Archaeological Science 35, 331–341, (2008). Silvestri, A., Molin, G. & Salviulo, G. Archaeological glass alteration products in marine and land-based environments: morphological, chemical and microtextural characterization. Journal of Non-Crystalline Solids 351, 1338–1349, (2005). Geisler, T. et al. Aqueous corrosion of borosilicate glass under acidic conditions: A new corrosion mechanism. Journal of Non-Crystalline Solids 356, 1458–1465, (2010). Schalm, O., Nuyts, G. & Janssens, K. Some critical observations about the degradation of glass: The formation of lamellae explained. Journal of Non-Crystalline Solids 569, (2021). Libourel, G. et al. The use of natural and archeological analogues for understanding the long-term behavior of nuclear glasses. Comptes Rendus Geoscience 343, 237–245, (2011). Weaver, J., MccLoy, J., Ryan, J. V. & Kruger, A. A. Ensuring longevity: Ancient glasses help predict durability of vitrified nuclear waste. American Ceramic Society Bulletin 95, 18–23, (2016). Sjöblom, R. et al. Assessment of the reason for the vitrification of a wall at a hillfort. The example of Broborg in Sweden. Journal of Archaeological Science: Reports 43, 103459, (2022). Plymale, A. E. et al. Niche Partitioning of Microbial Communities at an Ancient Vitrified Hillfort: Implications for Vitrified Radioactive Waste Disposal. Geomicrobiology Journal 38, 1–21, (2020). Englund, M. et al. Broborg Hillfort: A Research Study of the Vitrified Wall. The Archaeologists. Report No. 2018:103, (National Historical Museums, Stockholm, Sweden, 2018). Ogenhall, E. Amphibolitic rocks near Broborg, Uppland. Chemical and mineralogical analyses of metamorphic mafic-intermediate rocks from outcrops near the prehistoric vitrified Hhllfort Broborg and a boulder in the hillfort. Report No. RAÄ 156:1, (Arkeologerna, Uppland, Sweden, 2016). Kresten, P. & Ambrosiani, B. Swedish vitrified forts: a reconnaissance study. Fornvännen Journal of swedish antiquarian research 87, 1–17, (1992). McCloy, J. S. et al. Reproduction of melting behavior for vitrified hillforts based on amphibolite, granite, and basalt lithologies. Scientific Reports 11, 1272, (2021). Sjöström, J. K. et al. Late Holocene peat paleodust deposition in south-western Sweden-exploring geochemical properties, local mineral sources and regional aeolian activity. Chemical Geology 602, 120881, (2022). Swedish University of Agricultural Sciences (SLU). Digital soil map of Sweden , (2017). Ljungqvist, F. C. A new reconstruction of temperature variability in the extra-tropical Northern Hemisphere during the last two millennia. Geografiska Annaler: Series A, Physical Geography 92, 339–351, (2010). Gibbons, A. Why 536 was ‘the worst year to be alive' , (2018). Amundsen, B. & Baxilchuk, N. The long harsh Fimbul Winter is not a myth. Science Norway 24, (2019). Moberg, A. et al. Highly variable Northern Hemisphere temperatures reconstructed from low-and high-resolution proxy data. Nature 433, 613–617, (2005). Ilani, S., Flexer, A. & Kronfeld, J. Copper mineralization in sedimentary cover associated with tectonic elements and volcanism in Israel. Mineralium Deposita 22, (1987). Ben-Yosef, E. Back to Solomon's era: results of the first excavations at “Slaves' Hill”(site 34, Timna, Israel). Bulletin of the American Schools of Oriental Research 376, 169–198, (2016). Western, S. The Classificaiton of Arid Zone Soils. Journal of Soil Science 23, 279–297, (1972). Dan, J., Yaalon, D., Moshe, R. & Nissim, S. Evolution of Reg soils in southern Israel and Sinai. Geoderma 28, 173–202, (1982). Ravikovitch, S. Soil Map of Southern Israel (Hebrew University of Jerusalem Soil and Water Sciences, 1924). Dan, Y., Raz, Z., Yaalon, H. & Koyumdjisky, H. Soil Map of Israël. (Survey of Israel, 1975). International Union of Soil Science (IUSS). World Reference Base for Soil Resources. IUSS Working Group WRB, (2015). Cavanagh, M., Ben-Yosef, E. & Langgut, D. Fuel exploitation and environmental degradation at the Iron Age copper industry of the Timna Valley, southern Israel.. Scientific Reports 12, 15434, (2022). Rosen, S. A. Basic instabilities? Climate and culture in the Negev over the long term. Geomorphology 32, 6–22, (2017). Bruins, H. J. Ancient desert agriculture in the Negev and climate-zone boundary changes during average, wet and drought years: Ancient Agriculture in the Middle East. Journal of Arid Environments 86, 28–42, (2012). Alpert, P. et al. Climatic trends to extremes employing regional modeling and statistical interpretation over the E. Mediterranean. Global and Planetary Change 63, 163–170, (2008). Linneman, S. R. & Myers, J. D. Magmatic inclusions in the Holocene rhyolites of Newberry Volcano, central Oregon. Journal of Geophysical Research: Solid Earth 95, 17677–17691, (1990). MacLeod, N. S. & Sammel, E. Newberry Volcano, Oregon: a cascade range geothermal prospect. Oregon Geology 44, 123–131, (1982). Hildreth, W. Quaternary magmatism in the Cascades - Geologic perspectives. US Geological Survey Professional Paper, 1-125, (2007). Jensen, R. A., Donnelly-Nolan, J. M. & Mckay, D. A field guide to Newberry Volcano, Oregon . The Geological Society of America Field Guide 15 edn, (2009). Linneman, S. R., & Myers, J. D.. Magmatic inclusions in the Holocene rhyolites of Newberry volcano, central Oregon. Journal of Geophysical Research: Solid Earth 95, 17677–17691, (1990). USDA. Soil Survey Staff, Natural Resources Conservation Service , (2024). Mann, M. E., Zhang, Z., Hughes, M. K., Bradley, R. S., Miller, S. K., Rutherford, S., & Ni, F.. Global signatures and dynamical origins of the Little Ice Age and Medieval Climate Anomaly. Science 326, 1256–1260, (2009). Gedalof, Z. e., Mantua, N. J. & Peterson, D. L. A multi-century perspective of variability in the Pacific Decadal Oscillation: new insights from tree rings and coral. Geophysical Research Letters 29, (2002). Mote, P. W., Hamlet, A. F., Clark, M. P., & Lettenmaier, D. P.. Declining mountain snowpack in western North America. Bulletin of the American Meteorological Society 86, 39–49, (2005). Golovchak, R. et al. Remedial insight on ageing of glass through the study of ancient man-made artefacts. Archaeometry 63, 312–326, (2021). Angelini, I., Gratuze, B. & Artioli, G. in The Contribution of Mineralogy to Cultural Heritage (eds G. Artioli & R. Oberti) Glass and other vitreous materials through history 87–150 (Mineralogical Society, 2019). Furmanek, W. Antropoinfosfera współczesnego człowieka. Dydaktyka informatyki 8, 49–73, (2013). Furmanek, M. et al. Dobkowice revisited. Interdisciplinary research on an enclosure of the Jordanów culture. Anthropologie. International Journal of Human Diversity and Evolution 51, 375–396, (2014). Kuznicki, F. Soil Map of Poland [1:2,000,000] , (1984). Lamb, H. Climatic changes in our own times and future threats. Geography, 203–220, (1982). Perșoiu, A. et al. Holocene winter climate variability in Central and Eastern Europe. Scientific Reports 7, 1–8, (2017). Brázdil, R. et al. Historical climatology in Europe–the state of the art. Climatic Change 70, 363–430, (2005). Przybylak, R. Recent air-temperature changes in the Arctic. Annals of Glaciology 46, 316–324, (2007). Domonkos, P. et al. Variability of extreme temperature events in south–central Europe during the 20th century and its relationship with large-scale circulation. International Journal of Climatology: A Journal of the Royal Meteorological Society 23, 987–1010, (2003). Hand, R. J. The Ballidon glass burial experiment – 35 years on. Glass Technology 46, 237–242, (2005). McLoughlin, S. et al. The long term corrosion of glasses: analytical results after 32 years of burial at Ballidon. Glass Technology-European Journal of Glass Science and Technology Part A 47, 59–67, (2006). Namboodri Jr, C. & Wicks, G. SRL in-situ tests in the United Kingdom: Part 2, Surface analyses of SRS waste glass buried for one and two years in limestone at Ballidon, UK. Report No. WSRC-TP-91-288, (Savannah River Site, Aiken, SC, USA, 1991). United Kingdom Meteorlogical Office. UK Climate Averages for Nottingham , (2024). United Kingdom Soil Observatory (UKSO). Soil Map of Derbyshire , (2024). Hallett, S. H., Sakrabani, R., Keay, C. A. & Hannam, J. A. Developments in land information systems: examples demonstrating land resource management capabilities and options. Soil Use and Management 33, 514–529, (2017). Thorpe, C. et al. Insights into long-term glass corrosion mechanismsfrom the Ballidon project: a 50-year-old glass burialexperiment in an alkaline near surface environment. NPJ Materials Degradation, under review, (2024). Jantzen, C. M. et al. Performance of a buried radioactive high level waste (HLW) glass after 24 years. Journal of Nuclear Materials 378, 244–256, (2008). Wicks, G. G. US field testing programs and results. Journal of Nuclear Materials 298, 78–85, (2001). Weart, W. D. Evaluation of salt beds in New Mexico as a geologic repository for nuclear waste. [Waste Isolation Pilot Plant (WIPP)]. Report No. SAND-78-2086C, (Sandia Laboratory, Alburquerque, NM, USA, 1978). Bacon, D. et al. Field-Scale Lysimeter Studies of Low-Activity Waste Form Degradation. Report No. PNNL-27394, (Pacific Northwest National Laboratory, Richland, WA, USA, 2018). Neeway, J. J. et al. Review of intermediate-scale field tests in support of disposal of waste forms. Chemosphere 347, 140625, (2024). Geisler, T. et al. The mechanism of borosilicate glass corrosion revisited. Geochimica et Cosmochimica Acta 158, 112–129, (2015). Hellmann, R. in Encyclopedia of Glass Science, Technology, History, and Culture, Vol II (ed P. Richet) Corrosion of natural glasses in seawater 831–842 (The American Ceramic Society, 2021). Hellmann, R. in Encyclopedia of Glass Science, Technology, History, and Culture, Vol I (ed P. Richet) Mechanisms of glass corrosion by aqueous solutions 647–662 (The American Ceramic Society, 2021). Hellmann, R. et al. Nanometre-scale evidence for interfacial dissolution-reprecipitation control of silicate glass corrosion. Nature Materials 14, 307–311, (2015). Paudel, B. et al. ToF-SIMS in material research: A view from nanoscale hydrogen detection. Materials Today 75, 149–165, (2024). EPA – U.S. Environmental Protection Agency. SW-846 Test Method 3052: Microwave Assisted Acid Digestion of Siliceous and Organically Based Matrices. (U.S. Environmental Protection Agency, Washington, D.C, 1996). Fletcher, W. The chemical durability of glass. A burial experiment at Ballidon in Derbyshire. Journal of Glass Studies, 149–151, (1972). Ben-Yosef, E. & Rothenberg, B. Mining for ancient copper: Essays in memory of Beno Rothenberg . (Eisenbrauns, 2018). Hauptmann, A. Archaeometallurgy-Materials Science Aspects . (Springer, 2020). Avner, U. et al. Ancient copper mines at Nahal Amram, southern Arabah. Mining for Ancient Copper–Essays in Memory of Beno Rothenberg , 147–177, (2018). Rothenberg, B. Ancient copper industries in the western Arabah: an archaeological survey of the Arabah, Part 1. Palestine Exploration Quarterly 94, 5–71, (1962). Rothenberg, B. Archaeo-metallurgical researches in the southern Arabah 1959–1990. Part I: Late Pottery Neolithic to Early Bronze IV. Palestine Exploration Quarterly 131, 68–89, (1999). Barbana, F., Bertoncello, R., Milanese, L. & Sada, C. Alteration and corrosion phenomena in Roman submerged glass fragments. Journal of Non-Crystalline Solids 337, 136–141, (2004). Longinelli, A., Silvestri, A., Molin, G. & Salviulo, G. 1.8 ka old glass from the Roman ship Julia Felix : glass-water oxygen isotope exchange. Chemical Geology 211, 335–342, (2004). Matthews, B. E. et al. Micro- and Nanoscale Surface Analysis of Late Iron Age Glass from Broborg, a Vitrified Swedish Hillfort. Microscopy and Microanalysis 29, 50–68, (2023). Kresten, P., Kero, L. & Chyssler, J. Geology of the vitrified hill-fort Broborg in Uppland, Sweden. Geologiska Föreningen i Stockholm Förhandlingar 115, 13–24, (1993). Vicenzi, E. P. et al. Major to Trace Element Imaging and Analysis of Iron Age Glasses Using Stage Scanning in The Analytical Dual Beam Microscope (tandem). Heritage Science 10, 90, (2022). Marcial, J. et al. Effect of network connectivity on behavior of synthetic Broborg hillfort glasses. Journal of the American Ceramic Society 106, 1716–1731, (2023). US DOE. Performance Assessment for the Integrated Disposal Facility, Hanford Site. Report No. RPP-RPT-59958, Rev. 1, (Washington River Protection Solutions, LLC, Richland, WA, 2018). Bagwell, C. E. in Microbial biotechnology: energy and environment (ed Rajesh Arora) Going extreme for small solutions to big environmental challenges 363–381 (Savannah River National Laboratory, 2011). Weaver, J. L. et al. Microbial interactions with silicate glasses. npj Materials Degradation 5, 11, (2021). Foster, L. et al. Microbial bloom formation in a high pH spent nuclear fuel pond. Science of The Total Environment 720, 137515, (2020). Fredrickson, J. K. et al. Geomicrobiology of high-level nuclear waste-contaminated vadose sediments at the hanford site, washington state. Applied Environmental Microbiology 70, 4230–4241, (2004). U.S. DOE. Hanford Site Groundwater Monitoring Report for 2017. Report No. DOE/RL-2017-66, Rev. 0, (US Department of Energy, Richland Operations Office, Richland, Washington, USA, 2018). Kim, J.-S., Kwon, S.-K., Sanchez, M. & Cho, G.-C. Geological storage of high level nuclear waste. KSCE Journal of Civil Engineering 15, 721–737, (2011). Pierce, E. M. et al. Waste Form Release Data Package for the 2005 Integrated Disposal Facility Performance Assessment. Report No. PNNL-14805, (Pacific Northwest National Laboratory, Richland, WA, USA, 2004). Thorpe, C. L. et al. Microbial interactions with phosphorus containing glasses representative of vitrified radioactive waste. Journal of Hazardous Materials 462, 132667, (2024). Grahame, M. Charting the UK's changing climate, UK Meteorlogical Office News , (2021). Colman, S. M., Platt Bradbury, J. & Rosenbaum, J. G. Paleolimnology and paleoclimate studies in Upper Klamath Lake, Oregon. Journal of Paleolimnology 31, 129–138, (2004). Steinman, B. A. et al. 1,500 year quantitative reconstruction of winter precipitation in the Pacific Northwest. Proceedings of the National Academy of Sciences 109, 11619–11623, (2012). Büntgen, U. et al. 2500 Years of European Climate Variability and Human Susceptibility. Science 331, 578–582, (2011). Åberg, G. Precambrian geochronology of south-eastern Sweden. Geologiska Föreningen i Stockholm Förhandlingar 100, 125–154, (1978). Lundegardh, P. H. Petrology of the Uppsala Region Eastern Sweden. Swedish Geological Survey 544, 1–17, (1956). Katrantsiotis, C. Paleoenvironment and shore displacement since 3200 BC in the central part of the Långhundraleden Trail, SE Uppland Masters thesis, Stockholm University, (2013). Beyth, M., Segev, A. & Bartov, Y. Geological Map of Israel 1:50,000 Be'er Ora Sheet 25-IV. Geological Survey of Israel Maps, (1999). Mart, Y. & Horowitz, A. The tectonics of the Timna region in southern Israel and the evolution of the Dead Sea rift. Tectonophysics 79, 165–199, (1981). Garfunkel, Z. & Ben-Avraham, Z. The structure of the Dead Sea basin. Tectonophysics 266, 155–176, (1996). MacLeod, N. S., Sherrod, D. R., Chitwood, L. A., & Jensen, R. A.. Geologic map of Newberry volcano, Deschutes, Klamath, and Lake Counties, Oregon. Report No. I-2455 (Sheet 1 & 2). (1995). Hildreth, W. Quaternary magmatism in the Cascades—Geologic perspectives. US Geological Survey Professional Paper 1744, (2007). Priest, G. R. Volcanic and tectonic evolution of the Cascade volcanic arc, central Oregon. Journal of Geophysical Research: Solid Earth 95, 19583–19599, (1990). Bowles-Martinez, E. & Schultz, A. Composition of Magma and Characteristics of the Hydrothermal System of Newberry Volcano, Oregon, From Magnetotellurics. Geochemistry, Geophysics, Geosystems 21, e2019GC008831, (2020). Kondracki, J. Regional geography of Poland. PWN, Warsaw (in Polish) , (2002). Stevenson, I. & Gaunt, G. D. Geology of the country around Chapel en le Frith. Explanation of one-inch geological sheet 99, New Series. (1971). Hose, T. A. The English Peak District (as a potential geopark): Mining geoheritage and historical geotourism. Acta Geoturistica 8, 32–49, (2017). Dunham, K. A recent deep borehole near Eyam, Derbyshire. Nature Physical Science 241, 84–85, (1973). Additional Declarations No competing interests reported. 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Kruger","email":"","orcid":"","institution":"United States Department of Energy","correspondingAuthor":false,"prefix":"","firstName":"Albert","middleName":"A.","lastName":"Kruger","suffix":""}],"badges":[],"createdAt":"2025-01-01 01:23:04","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-5744111/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-5744111/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41529-025-00624-4","type":"published","date":"2025-08-05T15:58:08+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":73276442,"identity":"ad2d539b-5ecf-4b47-8b57-3c81642ad443","added_by":"auto","created_at":"2025-01-08 11:52:18","extension":"jpeg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":434683,"visible":true,"origin":"","legend":"\u003cp\u003eThe Integrated Disposal Facility (IDF) in the Central Plateau at the Hanford site\u003c/p\u003e","description":"","filename":"image1.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-5744111/v1/1c94ac99f003db6f6694f040.jpeg"},{"id":73276452,"identity":"276c7bed-9617-4732-955d-ec9bdc6f5907","added_by":"auto","created_at":"2025-01-08 11:52:19","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":16888497,"visible":true,"origin":"","legend":"\u003cp\u003eLocation of natural and archeological analogues sites. A) Hanford IDF, near Richland, WA, B) Newberry Volcano (Big Obsidian Flow), near Bend, Oregon, USA, C) Ballidon Experiment Site, Tarmac Quarry, Derbyshire, UK, D) Broborg Hillfort, Uppland, Sweden, E) Dobkowice Archeological Site, Lower Silesian Voivodeship, Poland, F), Timna Site (Slaves' Hill), Timna Valley, Israel. The overview image was created using ESRI ArcMap; all others were created using Google Earth.\u003c/p\u003e","description":"","filename":"image2.png","url":"https://assets-eu.researchsquare.com/files/rs-5744111/v1/50d189e89483fd45916ffde9.png"},{"id":73276447,"identity":"caf5fe75-2689-4363-8db6-27714494c206","added_by":"auto","created_at":"2025-01-08 11:52:18","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":483845,"visible":true,"origin":"","legend":"\u003cp\u003eTimeline showing relevant time periods and ages of analogues, redrawn from Weaver et al.\u003csup\u003e25\u003c/sup\u003e For sites with analogues from multiple time periods, a colored rectangle describes the minimum and maximum ages. The timeline is shown in years before present, with present defined as 2024.\u003c/p\u003e","description":"","filename":"image3.png","url":"https://assets-eu.researchsquare.com/files/rs-5744111/v1/ee8ea8b6a6fe7cbb35a829a0.png"},{"id":73276448,"identity":"2dbd64d4-aef8-4007-91ce-a3275c2df715","added_by":"auto","created_at":"2025-01-08 11:52:18","extension":"jpeg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":155863,"visible":true,"origin":"","legend":"\u003cp\u003eThree-dimensional reconstruction of XCT data from eleven Timna samples (A-K). The greyscale values in the individual images represent the relative attenuation of X-rays, which is a function of mass density.\u003c/p\u003e","description":"","filename":"image4.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-5744111/v1/0bad396351598b632c9777c4.jpeg"},{"id":73276453,"identity":"4418d5b3-7ad2-4fb8-ab0c-f513148226b1","added_by":"auto","created_at":"2025-01-08 11:52:19","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":20000381,"visible":true,"origin":"","legend":"\u003cp\u003eOptical microscopy images of eleven Timna samples (A-K).\u003c/p\u003e","description":"","filename":"image5.png","url":"https://assets-eu.researchsquare.com/files/rs-5744111/v1/681057fa03a451cf0249c9c2.png"},{"id":73277517,"identity":"5671fb79-e6c3-46de-b1e4-9e72e5e618dd","added_by":"auto","created_at":"2025-01-08 12:00:18","extension":"jpeg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":194650,"visible":true,"origin":"","legend":"\u003cp\u003eXRD patterns of Timna samples (A-K) after addition of a 5 wt.% CeO\u003csub\u003e2\u003c/sub\u003e internal standard. Q=quartz (SiO\u003csub\u003e2\u003c/sub\u003e), Fy=fayalite (Mg\u003csub\u003e\u003cem\u003ex\u003c/em\u003e\u003c/sub\u003eFe\u003csub\u003e\u003cem\u003e1-x\u003c/em\u003e\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003eSiO\u003csub\u003e4\u003c/sub\u003e, D=diopside (MgCaSi\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e6\u003c/sub\u003e), and B=birnessite (MnO\u003csub\u003e2\u003c/sub\u003e·\u003cem\u003en\u003c/em\u003eH\u003csub\u003e2\u003c/sub\u003eO)\u003c/p\u003e","description":"","filename":"image6.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-5744111/v1/02a683b9ee0834b0c095f311.jpeg"},{"id":73277526,"identity":"bd770e41-73fd-454b-8043-ed628d75969e","added_by":"auto","created_at":"2025-01-08 12:00:19","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":7748453,"visible":true,"origin":"","legend":"\u003cp\u003eA) Optical microscope image of partially vitrified Timna sample. B-C) SEM-BSE (backscatter electron) images of partially vitrified sample showing scale of surficial layer (denoted as “SL” in C). In B) a red arrow points from the approximate location of the elemental map shown in C).\u003c/p\u003e","description":"","filename":"image7.png","url":"https://assets-eu.researchsquare.com/files/rs-5744111/v1/ac62e4900e7d81839979ade3.png"},{"id":73276469,"identity":"05f1a50b-27da-4dd0-93bc-6d79c36d5af4","added_by":"auto","created_at":"2025-01-08 11:52:19","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":3597842,"visible":true,"origin":"","legend":"\u003cp\u003eToF-SIMS maps of partially vitrified Timna sample and corresponding SEM-BSE image of the same area\u003c/p\u003e","description":"","filename":"image8.png","url":"https://assets-eu.researchsquare.com/files/rs-5744111/v1/23cc084bcc44acd2ae421666.png"},{"id":73276466,"identity":"79328c0f-1401-4efc-98a3-9d27eb0ce3d4","added_by":"auto","created_at":"2025-01-08 11:52:19","extension":"jpeg","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":329031,"visible":true,"origin":"","legend":"\u003cp\u003eA) SEM-BSE image and B) higher magnification EPMA-WDS maps of a replica medieval glass sample excavated from the Ballidon site showing surface layer (SL) with prominent depletion-enrichment banding. Approximate boundaries are shown with dashed lines.\u003c/p\u003e","description":"","filename":"image9.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-5744111/v1/4379fd9d5bac17c56c590f2c.jpeg"},{"id":73276458,"identity":"f3071644-2e6b-4162-a710-5ef0b5df7be5","added_by":"auto","created_at":"2025-01-08 11:52:19","extension":"jpeg","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":196616,"visible":true,"origin":"","legend":"\u003cp\u003eA) SEM-BSE image of Dobkowice sample in cross-section B) SEM-BSE image showing two surficial layers (SL# 1 and 2) that formed during alteration. C) SEM-EDS map overlaid on SEM-BSE image showing complex microstructure in one portion of the surficial layer SL#1. The small Al-rich growths are considered equivalent to SL#2.\u003c/p\u003e","description":"","filename":"image10.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-5744111/v1/d2cac5fa9117f30892995695.jpeg"},{"id":73276478,"identity":"7e09a9ea-5408-47db-b046-be2a5505e976","added_by":"auto","created_at":"2025-01-08 11:52:20","extension":"jpeg","order_by":11,"title":"Figure 11","display":"","copyAsset":false,"role":"figure","size":474553,"visible":true,"origin":"","legend":"\u003cp\u003eSEM-BSE image and corresponding ToF-SIMS maps of the Dobkowice sample. The chemical maps show that principal alteration layer (SL#1) is enriched in H, Si, Ca, and just slightly in Mg, whereas Na, Al, and K are depleted. Arrows demarcate the SL#1-bulk glass interface. The thin outer rim (SL#2) is enriched in Al and K. The prominent crack is an artefact.\u003c/p\u003e","description":"","filename":"image11.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-5744111/v1/6f202ef943192e0879cbc457.jpeg"},{"id":73276479,"identity":"98234bde-00ff-4d39-8e18-444a411f5ba0","added_by":"auto","created_at":"2025-01-08 11:52:20","extension":"png","order_by":12,"title":"Figure 12","display":"","copyAsset":false,"role":"figure","size":8086474,"visible":true,"origin":"","legend":"\u003cp\u003eA) optical microscopy image of Broborg sample BB1b with red arrows showing the location mapped by SEM-EDS. B-C) SEM-EDS elemental maps overlaid on SEM-BSE. SL = surficial layer.\u003c/p\u003e","description":"","filename":"image12.png","url":"https://assets-eu.researchsquare.com/files/rs-5744111/v1/2578f5190af2f34c5789cac5.png"},{"id":73276465,"identity":"dc5b7acc-a1de-4837-b4b9-baad77d54ba2","added_by":"auto","created_at":"2025-01-08 11:52:19","extension":"jpeg","order_by":13,"title":"Figure 13","display":"","copyAsset":false,"role":"figure","size":359619,"visible":true,"origin":"","legend":"\u003cp\u003eSEM-EDS maps of Broborg sample BB1b showing a surficial layer (SL) that formed in contact with the mafic glass. The arrows indicate the interface between bulk glass and the SL.\u003c/p\u003e","description":"","filename":"image13.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-5744111/v1/94ce241115367272e028cdc3.jpeg"},{"id":73276459,"identity":"0521c808-6dd2-451f-a97f-9be24018b311","added_by":"auto","created_at":"2025-01-08 11:52:19","extension":"jpeg","order_by":14,"title":"Figure 14","display":"","copyAsset":false,"role":"figure","size":659690,"visible":true,"origin":"","legend":"\u003cp\u003eA), C), and E) photographs of Newberry obsidian samples MJS-1, BOF-9, and BOF-6. B), D), and F) corresponding cross-sectional SEM-EDS elemental maps of the surface regions and underlying matrix. (Individual EDS maps are provide in Figs. S3-S5)\u003c/p\u003e","description":"","filename":"image14.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-5744111/v1/4727f555b288a7bedf66ba46.jpeg"},{"id":73276456,"identity":"a925dd13-5b78-4bf6-8d17-b0dc7adf8e7f","added_by":"auto","created_at":"2025-01-08 11:52:19","extension":"jpeg","order_by":15,"title":"Figure 15","display":"","copyAsset":false,"role":"figure","size":78357,"visible":true,"origin":"","legend":"\u003cp\u003eSEM-BSE image and ToF-SIMS maps of Newberry obsidian sample, MJS-1\u003c/p\u003e","description":"","filename":"image15.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-5744111/v1/4d05e30bca69ad2963f47b31.jpeg"},{"id":88814245,"identity":"2f90b98a-eb54-4416-adec-59d49dc7e793","added_by":"auto","created_at":"2025-08-11 16:09:01","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":56495345,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-5744111/v1/2126c40d-a40c-4fd6-918e-12fb0b03e1d4.pdf"},{"id":73276445,"identity":"2d458c11-baf7-4b4e-a229-20789e1cc74c","added_by":"auto","created_at":"2025-01-08 11:52:18","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":7582195,"visible":true,"origin":"","legend":"","description":"","filename":"SUPPLEMENTARYMATERIAL.docx","url":"https://assets-eu.researchsquare.com/files/rs-5744111/v1/c841ede0a73633b0e14860fb.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Alteration of archeological and natural analogues for radioactive waste glass under different environmental conditions","fulltext":[{"header":"INTRODUCTION","content":"\u003cp\u003eGlass waste forms are required to safely dispose of radioactive waste by immobilizing radionuclides and mitigating their release into the environment. At the Hanford site, a Department of Energy legacy nuclear waste site in Washington state, USA, hundreds of thousands of cubic meters of legacy radioactive waste from plutonium production will be immobilized in glass, with low activity waste (LAW) glass disposed in a near surface integrated disposal facility (IDF). The glass must limit radionuclide release into the environment for thousands of years, which is challenging to assess in laboratory experiments. Central to radioactive waste management is to understand the corrosion processes and quantify the corrosion rates of the glass waste form. However, laboratory glass corrosion experiments have a limitation: their timeframes are considerably shorter than the timeframes over which radionuclides must be retained in a nuclear waste disposal site. Studies of natural analogues \u003csup\u003e\u003cspan additionalcitationids=\"CR2 CR3 CR4 CR5 CR6 CR7 CR8\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u003c/sup\u003e and anthropogenic glasses\u003csup\u003e\u003cspan additionalcitationids=\"CR11 CR12 CR13 CR14\" citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003e can help bridge this important gap. Using such glasses has significant theoretical and practical implications for the field of nuclear waste management. By validating models used to assess waste form behavior with findings from natural and anthropogenic glasses, we can better understand the long-term performance of nuclear waste glasses. The alteration environments for these glass analogues vary in terms of temperature, pore fluid chemistry and pH, solid surface area to liquid volume ratio, percolation rate, and soil microbial communities. These variables must be considered when comparing analogues with proposed nuclear waste glasses.\u003csup\u003e\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eNatural glass analogues such as basaltic glasses (45\u0026ndash;50 wt.% SiO\u003csub\u003e2\u003c/sub\u003e), tektites (65\u0026ndash;90% wt.% SiO\u003csub\u003e2\u003c/sub\u003e), and obsidian glasses (70\u0026ndash;75 wt.% SiO\u003csub\u003e2\u003c/sub\u003e) are found in the terrestrial environment. The thickness of the surface alteration layer can be used to semi-quantitatively evaluate the alteration rate of glasses.\u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e,\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e Research suggests that the alteration mechanisms of natural, anthropogenic, and nuclear glasses are similar.\u003csup\u003e\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u003c/sup\u003e Techer et al.\u003csup\u003e\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e compared the alteration of basaltic glass (ages ranging from several thousand to a few million years) in the natural environment with the alteration of basaltic glass and a reference nuclear waste glass (SON68) under laboratory conditions for periods of four days up to several hundred days. Techer et al.\u003csup\u003e\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e pointed out some uncertainties and assumptions for natural samples, for example, the uncertainty in the nature of the altering environment and glass-solution contact time, and the assumption that the palagonite (natural alteration product) thickness can be directly compared to alteration layer thicknesses measured on glasses corroded in laboratory experiments. However, the results suggest that the mean alteration rate estimated from measured palagonite thickness and the age of the natural glasses was comparable to rates measured in closed system laboratory experiments. It was hypothesized that this was due to the alteration products forming a protective layer on the glass surface.\u003csup\u003e\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eArchaeological glasses have also been used as analogues for comparison with nuclear waste glass.\u003csup\u003e\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u003c/sup\u003e While archeological analogues are not compositionally identical to natural and nuclear glasses, they do contain most of the same major elements (alkalis, Si, Al, Fe, etc.).\u003csup\u003e\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u003c/sup\u003e Archaeological glasses also meet the criteria for an analogue because information about the altering environment over the glass\u0026rsquo;s exposure time is often well documented. For example, two Roman glasses have been used as analogues to study long-term glass alteration behavior: 1) glass from a shipwreck off the coast of the Embiez Islands, France;\u003csup\u003e\u003cspan additionalcitationids=\"CR13\" citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u003c/sup\u003e 2) glass from the shipwreck \u003cem\u003eIulia Felix\u003c/em\u003e off the coast near Grado, Italy.\u003csup\u003e\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e,\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e,\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u003c/sup\u003e These two glasses with similar compositions were altered in marine environments for nearly 1800 years. The \u003cem\u003eEmbiez\u003c/em\u003e glass was altered in open water in the Mediterranean Sea (15\u0026deg;C). The \u003cem\u003eIulia Felix\u003c/em\u003e glass was altered in the Adriatic Sea (15\u0026deg;C), which has a slightly different chemistry than the Mediterranean, and was covered with sand during its alteration. The \u003cem\u003eEmbiez\u003c/em\u003e glass shows significant cracking due to fast cooling during its fabrication, and an alteration behavior that is dependent on the size of the cracks.\u003csup\u003e\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e The same cracking phenomenon is observed in nuclear waste glass fabrication. The glass from the \u003cem\u003eIulia Felix\u003c/em\u003e shipwreck contains both colored\u003csup\u003e\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u003c/sup\u003e and colorless fractions.\u003csup\u003e\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e\u003c/sup\u003e The two glasses have compositions that vary only slightly; however, alteration of the colorless glass results in an opaque white crust, composed mostly of silica (SiO\u003csub\u003e2\u003c/sub\u003e), while the colored fraction shows alteration layers consisting of repeating lamellae.\u003csup\u003e\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e\u003c/sup\u003e Lamellae have also been observed in static tests of nuclear waste glass in highly acidic conditions.\u003csup\u003e\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/sup\u003e This type of alteration has not been observed in laboratory testing at pH values near those expected in a disposal facility (pH 6\u0026ndash;9), but the pH dependence of this possible dissolution-precipitation mechanism needs to be confirmed.\u003csup\u003e\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eWaste glasses are typically subjected to short-term, accelerated laboratory tests to show they are chemically durable for long periods. The kinetic behavior of these accelerated laboratory tests is then extrapolated over long time periods and may not produce accurate predictions of glass durability over thousands of years. In addition, glass analogues have been used to predict the alteration of nuclear waste glasses during disposal in subsurface geological repositories.\u003csup\u003e\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e,\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e,\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e,\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e\u003c/sup\u003e In particular, natural and archeological glasses can be used to assess how the alteration layers on the glass may have formed in response to the near-field environmental conditions.\u003c/p\u003e \u003cp\u003eHere, we characterize natural and archaeological glasses from five near-surface sites exposed to different environmental conditions (e.g., average temperatures, extent of hydraulic saturation, etc.). A detailed description of the sites is provided, along with characterization data for the excavated samples. The range of environmental conditions covered by these sites is relevant to the disposal of radioactive LAW glass at the near-surface, hydraulically unsaturated IDF at the Hanford site.\u003c/p\u003e"},{"header":"DESCRIPTION OF SITES","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003eIntegrated Disposal Facility (IDF) for low-activity waste (LAW) glass\u003c/h2\u003e \u003cp\u003eUnlike highly radioactive material, which will be buried deep underground in stable rock formations in a geological disposal facility, low activity radioactive waste does not require shielding and is suitable for disposal in shallower facilities closer to the surface. The Integrated Disposal Facility (IDF) is intended to be a near-surface disposal facility for radioactive LAW glass at the Hanford Site (Figs.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e and \u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eA). It is a large, lined disposal trench excavated\u0026thinsp;~\u0026thinsp;13 m deep into the Hanford sands in the Central Plateau at the Hanford Site. The key engineered design features of the IDF consist of: (i) containers around the waste and a surface barrier placed above the waste limit water from contacting the waste; (ii) engineered backfill placed between and above waste containers to provide structural support after closure; (iii) borosilicate glass waste forms limit the release of contaminants due to the slow dissolution of the glass matrix. The key natural features consist of: (i) a semi-arid climate and shrub-steppe ecology that results in very little natural recharge to the groundwater due to low annual precipitation rates and high evapotranspiration; (ii) the thick vadose zone that delays the time it takes contaminants released from the source term to arrive at the saturated zone. The climate at the Hanford Site is mid-latitude semiarid desert. Daytime high temperatures in June, July, and August range from 17.2\u0026deg;C to 27.9\u0026deg;C but can exceed 40\u0026deg;C. During the winter, temperatures generally range from \u0026minus;\u0026thinsp;0.2\u0026deg;C to 6.9\u0026deg;C but can occasionally drop below \u0026minus;\u0026thinsp;18\u0026deg;C. The normal annual relative humidity is 54% and average annual precipitation is 17 cm. At the Hanford Site, basalt is underlain by Tertiary continental sedimentary rocks and overlain by late Tertiary and Quaternary fluvial and glacio-fluvial deposits. To establish limits on radionuclides that will be disposed of in the near-surface IDF, an assessment of impacts to groundwater resources must be made so that the concentration of radionuclides does not exceed the drinking water standard. To make this assessment, the alteration behavior of the LAW glass in the near surface environment of the IDF must be known.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003eAnalogue Site Similarities and Differences\u003c/h3\u003e\n\u003cp\u003eSamples were chosen from specific analogue sites to evaluate the following parameters: 1) how variation in surficial geology affects glass degradation; 2) effects of the environment on glass degradation; 3) comparison of sites with respect to the geology and current environment conditions, and possible environmental changes at the IDF; and 4) effect of hydraulic saturation (especially compared to the nominal conditions at the IDF). Several of these analogue glasses are from archeologically significant sites, therefore it was not possible to randomize sample collection, resulting in an unintentional bias towards sample types that were more widely available for characterization. The site characteristics, as detailed below, vary in terms of 1) the amount of time the glass was buried, 2) the chemical composition of the glass, 3) the surficial geology, 4) the environment (precipitation and climate), 5) burial depth, and 6) site elevation. Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e summarizes the analogue glasses chosen for study, Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e provides a map of the excavation sites, and Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e provides a timeline comparing relevant timescales (the alteration timescales for the analogue sites will be described in the subsequent sections). Information on the geologic setting for each site is available in the supplementary material.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eSummary of glasses and alteration environments\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSite\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eType of Glass\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eOrigin and Age (y)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eAnnual Precipitation (mm)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eAverage Air Temperature (\u0026deg;C)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eElevation\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eHanford, USA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eBorosilicate\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eWasteform for disposal of low activity radioactive waste, not yet produced\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e~\u0026thinsp;170\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e~\u0026thinsp;12\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003eIDF is 13 m deep, Hanford Site is 123 m above sea level\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eTimna, Israel\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eMelted granite, monzonite, monzodiorite, olivine norite, diorite, peridotite\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCopper slag, 1200\u0026ndash;6000\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e30\u0026thinsp;\u0026minus;\u0026thinsp;15\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e~\u0026thinsp;21\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e~\u0026thinsp;300\u0026ndash;450 m above sea level\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eBroborg, Sweden\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eDark glass from melted amphibolite, clear glass from melted granite\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eRocks melted in box-like structures around a hillfort, 1,500\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e700 \u0026minus;\u0026thinsp;750\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e~\u0026thinsp;4.6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e50 m above sea level/ near watershed\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eBallidon, UK\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eSimulant Roman, Medieval, borosilicate, plate glass, soda lime, E-glass and lead optical\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eExperiment to understand glass corrosion under alkaline conditions, 50\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e908\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e9.2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003eBuried in a model burial mound comprised of limestone fragments, 282 m above sea level\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eNewberry, USA\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eObsidian, basalt, andesite, rhyolite, and pumice\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eLast volcanic eruption: Big Obsidian Flow (BOF), ~ 1300\u0026ndash;1400\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e~\u0026thinsp;900\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003eOn top of the BOF, 2433 m above sea level\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDobkowice, Poland\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eSoda-lime-silica glass\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eGlass bead, 2600\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e700 mm\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0\u0026deg;C\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003eBuried in grave\u0026thinsp;~\u0026thinsp;1 m deep, 110 m above sea level\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e\n\u003ch3\u003eBroborg Sweden\u003c/h3\u003e\n\u003cp\u003eBroborg (59\u0026deg;45\u0026rsquo;20\u0026rdquo; N, 17\u0026deg;57\u0026rsquo;06\u0026rdquo; E, elevation 49 m) Viking hillfort (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eE) was established\u0026thinsp;~\u0026thinsp;375\u0026ndash;550 CE and used for approximately 175 years\u003csup\u003e\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u003c/sup\u003e in what is now the southeastern Uppland Province, ~ 25 km southeast of Uppsala. The technology and materials used to construct this hillfort are summarized by Sj\u0026ouml;blom et al.\u003csup\u003e\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e\u003c/sup\u003e Vitrified rock samples were collected from the Broborg site during multiple excavations (1982-83, 1990 and 2017) described elsewhere.\u003csup\u003e\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e,\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u003c/sup\u003e Bulk sample analyses of the granite and amphibolite rocks were presented by Ogenhall.\u003csup\u003e\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e\u003c/sup\u003e Vitrified materials from the Broborg site were produced when the local amphibolite and granite were melted \u003cem\u003ein situ\u003c/em\u003e.\u003csup\u003e\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e,\u003cspan additionalcitationids=\"CR31\" citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u003c/sup\u003e The vitrification of the amphibole-rich rock produced a dark Fe and Mg-rich glass, while vitrification of the granite yielded a clear Na and Si-rich glass. The surficial layers observed on excavated samples were compared to surficial layers observed on excavated material that had been remelted to form coupons which, in turn, were subjected to laboratory testing (vapor hydration test, VHT, product consistency test, PCT, and EPA method 1313).\u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eBroborg\u0026rsquo;s selection as an analogue site provided an opportunity to study ancient glass buried in a soil that is a mixture of ancient mountain soil and more recent till-derived sandy clay loam.\u003csup\u003e\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e\u003c/sup\u003e The overall climate of this site can be characterized as relatively humid and continental. Before the hillfort was constructed, temperatures were slightly warmer than the long-term average in the Roman Warm Period\u003csup\u003e\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u003c/sup\u003e (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). When the fort was active, the Dark Age Cold Period (ca. 300\u0026ndash;800 CE) was marked by temperatures below the long-term average.\u003csup\u003e\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u003c/sup\u003e Volcanism in Iceland caused temperatures to plummet from 536 to 539 CE.\u003csup\u003e35 36\u003c/sup\u003e The Medieval Warm Period saw an increase of 0.3 to 1.1\u0026deg;C compared to the local maximum. After the maximum, another cooling trend occurred during the Little Ice Age (LIA) before reversing around 1600 CE with warming to 2000 CE.\u003csup\u003e\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e,\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\n\u003ch3\u003eTimna, Israel\u003c/h3\u003e\n\u003cp\u003eTimna (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eF), situated in the Aravah valley of the southern Negev desert (Israel), is known for its well-preserved historic copper mining districts that reveal at least 7000 years of archeological evidence of metallurgical activity. The region's tectonic and hydrothermal activities, combined with the specific rock types, contributed to the formation of copper deposits.\u003csup\u003e\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u003c/sup\u003e Ancient smelting sites provide evidence for copper production from the Copper Age to the Early Islamic Period. The vitrified slag samples from Timna described in the present paper were retrieved from copper smelting sites from the Early Bronze Age to the Early Islamic Age.\u003csup\u003e\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e\u003c/sup\u003e Timna's primarily hot desert climate and arid soils contrast starkly with those of the other analogue sites. The dominant soils in Timna are aridisols.\u003csup\u003e\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e,\u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e\u003c/sup\u003e These are dry soils with limited organic matter and weak soil structure. Due to low rainfall and high evaporation rates, they are often saline.\u003csup\u003e\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e,\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e,\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e\u003c/sup\u003e Due to the limestone and chalk bedrock in regions around Timna, some soils exhibit a high calcium carbonate content, which can form hardpans or caliche layers.\u003csup\u003e\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eHyper-arid conditions have dominated the Aravah Valley\u003csup\u003e\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e,\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e\u003c/sup\u003e, due to it being located in the rain shadow of the Negev Highlands.\u003csup\u003e\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e,\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e\u003c/sup\u003e The middle Holocene experienced significant climate fluctuations, ranging from hyper-arid periods to intervals with higher levels of precipitation.\u003csup\u003e\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e\u003c/sup\u003e This was superseded by drier conditions with fewer oscillations in rainfall in the late Holocene. In the Middle Bronze Age to the end of the Late Bronze Age, humidity increased, followed by a sudden and pronounced\u0026thinsp;~\u0026thinsp;150-year dry event occurring from 1300 to 1200 BCE.\u003csup\u003e\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e\u003c/sup\u003e The LIA was marked by increased aridity encompassing the Near East.\u003csup\u003e\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e,\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e\u003c/sup\u003e In the modern era, climate change has impacted Timna. The 20th and 21st centuries have seen a general trend of increasing temperatures, with precipitation patterns becoming more unpredictable and extreme.\u003csup\u003e\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\n\u003ch3\u003eNewberry, Oregon, USA\u003c/h3\u003e\n\u003cp\u003eNewberry Volcano, near Bend in central Oregon and east of the Cascade Range on the western edge of the High Lava Plains, is one of the largest and most active volcanoes in the contiguous United States. Samples were collected in 2021 from Newberry\u0026rsquo;s Big Obsidian Flow (BOF) (43\u0026deg;41\u0026rsquo;36\u0026rdquo; N, 121\u0026deg;13\u0026rsquo;45\u0026rdquo; W, elevation 2206 m) (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eB). Newberry last erupted\u0026thinsp;~\u0026thinsp;1,350 years ago (i.e., ~\u0026thinsp;675 CE), resulting in the BOF.\u003csup\u003e\u003cspan additionalcitationids=\"CR50 CR51\" citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e52\u003c/span\u003e\u003c/sup\u003e The obsidian from the most recent flow contained 72.8 wt.% SiO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e53\u003c/sup\u003e and differed from most other rhyolitic rocks on the Newberry volcano in their much higher Rb/Sr ratio.\u003csup\u003e\u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eNewberry samples were chosen for this study due to their natural origin, unique chemical composition, and differing climate. The soils that contact the BOF are andisols. They are primarily derived from volcanic materials and tend to have a loamy texture with a balance of sand, silt, and clay, thereby allowing good water infiltration and root penetration.\u003csup\u003e\u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e54\u003c/span\u003e\u003c/sup\u003e During the Medieval Climate Anomaly (MCA), the Newberry region experienced warmer and drier conditions.\u003csup\u003e\u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e55\u003c/span\u003e\u003c/sup\u003e During the LIA, cooler temperatures prevailed, with more frequent and extended wet periods influencing the region's ecosystems and human settlements.\u003csup\u003e\u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e56\u003c/span\u003e\u003c/sup\u003e Following the LIA, Newberry and Pacific Northwest regions' temperatures began to rise. The 20th and 21st centuries have seen an acceleration of this warming trend, consistent with global climate change patterns. Recent studies have shown a decline in snowpack levels in the Oregon Cascades and a trend toward earlier spring snowmelt.\u003csup\u003e\u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e,\u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e53\u003c/span\u003e,\u003cspan citationid=\"CR57\" class=\"CitationRef\"\u003e57\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003eDobkowice, Poland\u003c/h2\u003e \u003cp\u003eDobkowice is a town in Jarosław county of Poland\u0026rsquo;s Subcarpathian province, situated atop the northern edge of the Carpathian Foredeep geological basin. Approximately 30 glass beads and other artifacts from the Bronze age were excavated from a crematory gravesite (49\u0026deg;55'48.92\" N 22\u0026deg;42'55.85\" E, elevation 218 m) (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eE)\u003csup\u003e\u003cspan citationid=\"CR58\" class=\"CitationRef\"\u003e58\u003c/span\u003e\u003c/sup\u003e. The glass beads were made using a mixture of natron and lime, or shells with sand.\u003csup\u003e\u003cspan citationid=\"CR59\" class=\"CitationRef\"\u003e59\u003c/span\u003e\u003c/sup\u003e Because of their soda-lime-silica composition, these glasses are commonly referred to as natron glass or low magnesium glass (LMG). The beads, relics of the Jordan\u0026oacute;w culture, are estimated to be ~\u0026thinsp;2600 years old (i.e., ~\u0026thinsp;430\u0026thinsp;\u0026plusmn;\u0026thinsp;150 BCE) and vary in color from light green to light brown.\u003csup\u003e\u003cspan citationid=\"CR58\" class=\"CitationRef\"\u003e58\u003c/span\u003e\u003c/sup\u003e A local farmer discovered the site in 1971 a few hundred meters northwest of the town. Excavations were conducted in the 1970s and 1980s, and finally in 2011\u0026ndash;2012 before construction of a highway began.\u003csup\u003e\u003cspan citationid=\"CR60\" class=\"CitationRef\"\u003e60\u003c/span\u003e,\u003cspan citationid=\"CR61\" class=\"CitationRef\"\u003e61\u003c/span\u003e\u003c/sup\u003e The Dobkowice site offers an opportunity to investigate anthropogenic glass buried in saturated soil in a relatively wet environment. The soil of the Dobkowice archeological site is an eutric fluvisol (soil base of saturation\u0026thinsp;\u0026gt;\u0026thinsp;50%).\u003csup\u003e62\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eDuring the so-called Roman Warm Period (RWP) period (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e), Poland, along with the rest of Europe, likely experienced warmer climates,\u003csup\u003e\u003cspan citationid=\"CR63\" class=\"CitationRef\"\u003e63\u003c/span\u003e\u003c/sup\u003e with relatively colder and drier winters offset by warmer and wetter summers.\u003csup\u003e\u003cspan citationid=\"CR64\" class=\"CitationRef\"\u003e64\u003c/span\u003e\u003c/sup\u003e After the RWP, a cold period that lasted until about 800 CE brought cooler temperatures. During the last\u0026thinsp;~\u0026thinsp;1000 years, until 1860 CE, summers and winters were colder than in previous millennia.\u003csup\u003e\u003cspan citationid=\"CR64\" class=\"CitationRef\"\u003e64\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eThe Medieval Climatic Anomaly (MCA), or Medieval Warm Period, was characterized by a warmer phase with temperatures that may have resembled modern pre-industrial times (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e).\u003csup\u003e\u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e55\u003c/span\u003e\u003c/sup\u003e During the LIA, Poland and its surrounding areas experienced significantly colder winters and summers, which profoundly affected agriculture, settlements, and even warfare.\u003csup\u003e\u003cspan citationid=\"CR65\" class=\"CitationRef\"\u003e65\u003c/span\u003e\u003c/sup\u003e Post-LIA warming was observed in Dobkowice and the surrounding region. In the 20th century, warming accelerated due to anthropogenic factors.\u003csup\u003e\u003cspan citationid=\"CR66\" class=\"CitationRef\"\u003e66\u003c/span\u003e\u003c/sup\u003e In recent decades, Poland has experienced higher temperatures, changes in precipitation, and increased extreme weather events such as heat waves and heavy rains, with an overall trend of rapid warming.\u003csup\u003e\u003cspan citationid=\"CR67\" class=\"CitationRef\"\u003e67\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003eBallidon, UK\u003c/h3\u003e\n\u003cp\u003eThe Ballidon quarry site offers a controlled environment allowing the study of both natural and anthropogenic glasses. The Ballidon glass burial experiment (53\u0026deg;05\u0026rsquo;38\u0026rsquo;N, 1\u0026deg;42\u0026rsquo;08\u0026rdquo; W, elevation 228 m) (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eC) was initiated in 1963, based on preliminary results from buried glass samples from the Experimental Earthworks in Wareham.\u003csup\u003e\u003cspan citationid=\"CR68\" class=\"CitationRef\"\u003e68\u003c/span\u003e\u003c/sup\u003e Various glasses were buried, including replica Roman soda\u0026ndash;lime\u0026ndash;silica glass, potash\u0026ndash;lime\u0026ndash;silica circa 17th century, and medieval glass.\u003csup\u003e\u003cspan citationid=\"CR69\" class=\"CitationRef\"\u003e69\u003c/span\u003e\u003c/sup\u003e The pore water pH conditions at Wareham were acidic, so the degradation of the glass samples was slow. In order to speed up the corrosion process and thus produce measurable effects over the short term, it was decided to bury an identical selection of glass samples in an alkaline environment (i.e., glasses buried in a limestone quarry).\u003csup\u003e\u003cspan citationid=\"CR68\" class=\"CitationRef\"\u003e68\u003c/span\u003e,\u003cspan citationid=\"CR70\" class=\"CitationRef\"\u003e70\u003c/span\u003e\u003c/sup\u003e. Samples at Ballidon were placed in a burial site originally measuring 3.5 m \u0026times;1.5 m and covered in limestone fragments, comprising of pieces of crushed limestone (1 cm \u0026minus;\u0026thinsp;8 cm fragments of calcite).\u003csup\u003e\u003cspan citationid=\"CR71\" class=\"CitationRef\"\u003e71\u003c/span\u003e\u003c/sup\u003e At a sample depth of \u0026lt;\u0026thinsp;20 cm, samples may occasionally have been affected by severe frosts. The soils at the Ballidon are loamy brown peaty topsoils underlain by clay subsoils, with an average pore water pH of 9.6.\u003csup\u003e\u003cspan citationid=\"CR72\" class=\"CitationRef\"\u003e72\u003c/span\u003e,\u003cspan citationid=\"CR73\" class=\"CitationRef\"\u003e73\u003c/span\u003e\u003c/sup\u003e Over the past 50 years, Derbyshire's climate has become slightly warmer and wetter, paralleling broader climatic trends across the UK.\u003csup\u003e\u003cspan citationid=\"CR71\" class=\"CitationRef\"\u003e71\u003c/span\u003e\u003c/sup\u003e According to the UK Meteorological Office, the average temperature in the UK increased around 0.8\u0026deg;C between 1961\u0026ndash;1990 and 1991-2020.\u003csup\u003e\u003cspan citationid=\"CR71\" class=\"CitationRef\"\u003e71\u003c/span\u003e\u003c/sup\u003e This increase was most substantial in central and eastern England, where some areas saw temperatures rise by more than 1.0\u0026deg;C.\u003csup\u003e\u003cspan citationid=\"CR71\" class=\"CitationRef\"\u003e71\u003c/span\u003e\u003c/sup\u003e Despite elevated precipitation conditions, there are intermittent drying periods during the summer months. These fluctuating environmental conditions, as compared to other disposal sites, may be responsible for their unique alteration signatures.\u003csup\u003e\u003cspan citationid=\"CR74\" class=\"CitationRef\"\u003e74\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eThe experiment was planned to run for 512 years, with the extraction of samples from sites within the mound at increasingly-spaced time intervals: 1, 2, 4, 8, 16, 32, 64, 128, 256 and 512 years.\u003csup\u003e\u003cspan citationid=\"CR68\" class=\"CitationRef\"\u003e68\u003c/span\u003e\u003c/sup\u003e The 64-year sample retrieval was brought forward in time due to interest in nuclear waste-form glasses. From 1986 onwards, simulant nuclear waste glasses, including glass formulations from the UK, USA, and Russia, have been buried in vacant sites at Ballidon for various periods of time.\u003c/p\u003e \u003cp\u003eSimilar glass burial experiments have also been undertaken elsewhere, including Chalk River Nuclear Laboratories (CRNL) in Ontario, Canada (1959\u0026ndash;1978),\u003csup\u003e\u003cspan citationid=\"CR75\" class=\"CitationRef\"\u003e75\u003c/span\u003e\u003c/sup\u003e the Stripa granite mine, Sweden (1982),\u003csup\u003e\u003cspan citationid=\"CR76\" class=\"CitationRef\"\u003e76\u003c/span\u003e\u003c/sup\u003e the Boom clay in Mol, Belgium (1986),\u003csup\u003e\u003cspan citationid=\"CR76\" class=\"CitationRef\"\u003e76\u003c/span\u003e\u003c/sup\u003e the halite disposal facility at the waste isolation pilot plant (WIPP) at Carlsbad, New Mexico (1986),\u003csup\u003e\u003cspan citationid=\"CR77\" class=\"CitationRef\"\u003e77\u003c/span\u003e\u003c/sup\u003e and the Hanford lysimeter site (present day) in glacial lake deposits and gravel.\u003csup\u003e\u003cspan citationid=\"CR78\" class=\"CitationRef\"\u003e78\u003c/span\u003e\u003c/sup\u003e To directly compare the effects of local environmental factors on glass alteration, the same simulant nuclear waste glasses have been buried at the Stripa, Mol, Ballidon, Carlsbad, and Hanford sites.\u003csup\u003e\u003cspan citationid=\"CR76\" class=\"CitationRef\"\u003e76\u003c/span\u003e\u003c/sup\u003e A discussion of other near-surface burial sites is provided elsewhere.\u003csup\u003e\u003cspan citationid=\"CR79\" class=\"CitationRef\"\u003e79\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e"},{"header":"RESULTS","content":"\u003cp\u003eAnalyses were performed on analogue samples from the five sites, and results are discussed in terms of the chemistry of the analog glasses, followed by observations and measurements of the surficial alteration layers prepared in cross section (or in some cases, ‘as-is’). Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e provides measured bulk compositions for samples from the five sites. These bulk compositions were measured using either EPMA or ICP-OES and ICP-MS following chemical digestion.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e\u003cdiv class=\"gridtable\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c9\" colnum=\"9\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c10\" colnum=\"10\"\u003e\u003c/div\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eComparison of select site sample compositions\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e\u003ccolgroup cols=\"10\"\u003e\u003c/colgroup\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eComponent\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eMJS1\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eBB1b (Na/Si-enriched)\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eBB1b (Mg/Fe-enriched)\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eDobkowice\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eReplica medieval glass (Hangleton)\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eTimna tuyère\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c8\"\u003e \u003cp\u003eSite 28 (representative of Timna samples A-G)\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c9\"\u003e \u003cp\u003eSite 201 (Timna sample H)\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c10\"\u003e \u003cp\u003eSite 34 (Timna samples I-K)\u003c/p\u003e \u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eLocation\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eNewberry\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e \u003cp\u003eBroborg\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eDobkowice\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003eBallidon\u003csup\u003e\u003cspan citationid=\"CR86\" class=\"CitationRef\"\u003e86\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colspan=\"4\" nameend=\"c10\" namest=\"c7\"\u003e \u003cp\u003eTimna\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSiO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e70.14\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e64.26\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e53.86\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e75.08\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e46.5\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e60.88\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e55.89\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e77.76\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e56.45\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAl\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e13.93\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e15.82\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e12.77\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.36\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e3.5\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e19.60\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.89\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e8.78\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e1.03\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eNa\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e4.76\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e3.70\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e2.78\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e17.76\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.7\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.57\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.44\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.47\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e0.55\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e3.48\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e5.25\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e12.83\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.17\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.2\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e11.04\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e21.5\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e6.4\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e22.76\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCaO\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.88\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e3.33\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e8.73\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e7.29\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e21.6\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e2.21\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e5.07\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e1.19\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e1.53\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eK\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e4.04\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e4.81\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1.39\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.11\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e16.4\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.63\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.92\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e1.14\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e1.25\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMgO\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.22\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.97\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e6.68\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.36\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e5.4\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.70\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.79\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.26\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e0.38\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMnO\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.10\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.43\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.02\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e1.71\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.01\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e4.73\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eP\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e5\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.58\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.20\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.06\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e4.6\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.18\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.67\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.08\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e1.88\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eTiO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.22\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.04\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.89\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.91\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.2\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e1.78\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e0.31\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZrO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.08\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.06\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.04\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e0.11\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCuO\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0.05\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e5.03\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.16\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e1.98\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eBaO\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.09\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.01\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e0.33\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCr\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0.03\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0.01\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e0.02\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCl\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1.01\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eOthers\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.32\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e0\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e6.71\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e1.91\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e6.69\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eTotal\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e97.74\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e100.87\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e100.38\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e102.53\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e99.9\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e97.786\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e \u003cp\u003e100\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMethod\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colspan=\"6\" nameend=\"c7\" namest=\"c2\"\u003e \u003cp\u003eEPMA\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colspan=\"3\" nameend=\"c10\" namest=\"c8\"\u003e \u003cp\u003eChemical digestion, ICP-OES, ICP-MS\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/table\u003e\u003c/div\u003e \u003cp\u003e\u003c/p\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003eTimna\u003c/h2\u003e \u003cp\u003eFor the samples that were excavated from Timna, the twelve samples chosen for analysis were biased toward material with high glass contents. These twelve analogues include eleven glassy slag samples and one tuyère sample that were taken from three smelting sites in or near the Timna Valley: site 28, site 34, and site 201. The tuyère sample (Site 34) is approximately 3150 years old.\u003csup\u003e\u003cspan citationid=\"CR87\" class=\"CitationRef\"\u003e87\u003c/span\u003e\u003c/sup\u003e The tuyère was a ceramic nozzle forming part of the bellows that were placed inside the furnace, usually pointing down to direct a forced draught towards the lower charcoals. The tuyère withstood extreme heat inside the furnace, with the area around reaching temperatures of approximately 1300–1500°C, allowing for molten metallurgical slag to accumulate on the tuyère, which mostly vitrified on cooling.\u003csup\u003e\u003cspan citationid=\"CR88\" class=\"CitationRef\"\u003e88\u003c/span\u003e\u003c/sup\u003e Site 28, named the Be’er Ora “Slag Valley”, was a big smelting camp located south of Timna Valley. Radiocarbon dating of samples from site 28 found that these materials mostly dated to the 7th -10th centuries CE.\u003csup\u003e\u003cspan additionalcitationids=\"CR90\" citationid=\"CR89\" class=\"CitationRef\"\u003e89\u003c/span\u003e–\u003cspan citationid=\"CR91\" class=\"CitationRef\"\u003e91\u003c/span\u003e\u003c/sup\u003e Site 34, named “Slaves Hill”, has been the central site of the Central Timna Valley (CTV) project that has been led by Tel Aviv University. It was excavated between 2012 and 2023 and has received the most attention of all Timna sites. Radiocarbon dating revealed that smelting occurred roughly between the late 11th and 10th centuries BCE.\u003csup\u003e\u003cspan citationid=\"CR87\" class=\"CitationRef\"\u003e87\u003c/span\u003e\u003c/sup\u003e Site 201 is located on top of a small hill on the western side of the Aravah, just 5 km north of Timna Valley. The CTV Project excavated Site 201 in 2020 to further understand technological developments associated with the very early history of extractive metallurgy. Radiocarbon dating suggests that the site was active at several periods, from the end of the late Copper (4000 BCE) to the Early Bronze Age.\u003c/p\u003e \u003cp\u003eTable\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e compares the amorphous contents of twelve Timna samples determined by XCT and XRD (using semi-quantitative Rietveld refinement) and lists the approximate ages of the samples. Figures\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e and \u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e show XCT reconstructions and optical micrographs of eleven Timna samples, while Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e shows the corresponding XRD patterns. Overall, the more recent samples exhibit larger amorphous contents, which is attributed to improvement in the melting technology with time leading to faster heating and cooling rates in the furnace.\u003c/p\u003e \u003cp\u003eAll the Timna samples show a thin surficial coating. The surficial layer on the tuyère sample, which is the sample containing the highest glass content, is not visible along the entire surface, but has a consistent thickness in the regions where it is observed. Figure\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e shows a ~ 2 µm thick surficial layer on a Timna sample obtained using SEM. The back scattered electron (BSE) image shows heterogeneities in mass-density within the layer, which is particularly noticeable when compared to the uniform unaltered bulk material. Silicon shows no major change in concentration, whereas Mg is enriched in the layer. The interfacial gradient in the Mg concentration, at the scale of the image, is relatively sharp. The bulk region does show a few white circular regions, whose origin is not known. It is interesting that these circular areas are enriched in Cu and depleted in Si. There is also a very thin dark band of material (i.e., elevated mass-density) at the inner boundary between the surficial layer and the bulk. Both the inner and outer interfaces of the dark band are very sharp.\u003c/p\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e shows the same area measured by ToF-SIMS. The elemental maps show that the surficial layer has a constant thickness (~ 2–3 µm) and is enriched in H, Mg, Al, Si, K, and Cu (Cu just slightly), and depleted in Na and Ca. All enriched elemental maps (including Ca) display some heterogeneity, characterized by small, localized areas with higher-than-average concentrations. The surficial layer has an additional and extremely thin but non-continuous external layer that shows even higher enrichment in Mg, Al, Si, and K. This very thin layer is also evident in the SEM-BSE image of Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e. Both the chemical maps and the BSE image show the same thin band at the inner boundary that separates the surficial layer from the bulk (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e). This black band may point to a physical gap, suggesting that the layer is not strongly bound to the bulk material.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e\u003cdiv class=\"gridtable\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e\u003ctable float=\"Yes\" id=\"Tab3\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eComparison of amorphous contents (measured by XCT and XRD) and sample ages for twelve Timna samples\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e\u003ccolgroup cols=\"6\"\u003e\u003c/colgroup\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eXCT solid inclusions volume fraction\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eXCT Amorphous volume fraction\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eXRD amorphous mass fraction\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eApproximate Sample age (years)\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eSample Location\u003c/p\u003e \u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eTimna-A\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e3.1%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e96.9%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e91.1%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1200 ± 150\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\" morerows=\"6\" rowspan=\"7\"\u003e \u003cp\u003eSite 28\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eTimna-B\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.1%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e99.9%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e92.8%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1200 ± 150\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eTimna-C\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.1%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e99.9%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e97.7%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1200 ± 150\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eTimna-D\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.1%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e99.9%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e99.3%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1200 ± 150\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eTimna-E\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.1%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e99.9%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e90.8%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1200 ± 150\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eTimna-F\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.1%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e99.9%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e89.8%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1200 ± 150\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eTimna-G\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.1%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e99.9%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e97.8%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1200 ± 150\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eTimna-H*\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u0026gt; 90%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eBQL\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e21.7%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e3100 ± 100\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003eSite 34\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eTuyère\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eN/A\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eN/A\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eN/A\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eN/A\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eTimna-I\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u0026gt; 90%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eBQL\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e12.8%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e4500 ± 200\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\" morerows=\"2\" rowspan=\"3\"\u003e \u003cp\u003eSite 201\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eTimna-J\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u0026gt; 90%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eBQL\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e8.3%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e4500 ± 200\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eTimna-K\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u0026gt; 90%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eBQL\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e23.0%\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e4500 ± 200\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colspan=\"6\" nameend=\"c6\" namest=\"c1\"\u003e \u003cp\u003eBQL = below quantitative limit\u003c/p\u003e \u003cp\u003e*indicates sample matrix appeared homogeneous by XCT but featured crystalline phases of size smaller than the minimum voxel size\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/table\u003e\u003c/div\u003e \u003cp\u003e\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec12\" class=\"Section2\"\u003e \u003ch2\u003eBallidon\u003c/h2\u003e \u003cp\u003eResults are presented for a replica medieval glass sample (of potassium-lime-silica composition, designed to replicate a specific glass known as the “Hangleton linen smoother”\u003csup\u003e\u003cspan citationid=\"CR86\" class=\"CitationRef\"\u003e86\u003c/span\u003e\u003c/sup\u003e) excavated from the Ballidon experimental mound.\u003csup\u003e\u003cspan citationid=\"CR74\" class=\"CitationRef\"\u003e74\u003c/span\u003e\u003c/sup\u003e This sample was altered under near-surface conditions for a duration of 52 years before retrieval. The sample was mounted in epoxy and analyzed using EPMA. Figure\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e shows SEM-BSE images and elemental maps of the altered surface layer (SL) of the replica medieval glass sample. After 52 years, the alteration layer on this sample is considerably thicker than those on the Timna samples, ranging from 400 µm to 1000 µm. The SL is not homogeneous but appears to change abruptly in the sub-layer adjacent to the soil, with respect to the presence of gaps or pores between the much thinner layers. The elemental distributions of the various elements show an alternating pattern of bands corresponding to element depletion and enrichment. The SL, furthest from the pristine glass, appears more chemically separated (‘banded’) whilst the younger alteration next to the pristine glass appears more uniform. The bands of enrichment and depletion also appear to be anti-correlated. Using the fiducial (red line) shown in panel B as a guide, the bands enriched in Al, Si, and possibly K are spatially correlated with the same bands showing depletion in Ca, P, Fe, and Mg (panel C). The chemical boundaries of the bands are relatively sharp, except for Na and K, which are in part indistinct. The band widths vary in thickness (10–25 µm), which is particularly evident in the Fe, Si, P, and Ca maps. Such banding was also present in the Roman glass from the \u003cem\u003eIulia Felix\u003c/em\u003e shipwreck. \u003csup\u003e\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e,\u003cspan citationid=\"CR92\" class=\"CitationRef\"\u003e92\u003c/span\u003e,\u003cspan citationid=\"CR93\" class=\"CitationRef\"\u003e93\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec13\" class=\"Section2\"\u003e \u003ch2\u003eDobkowice\u003c/h2\u003e \u003cp\u003eAn SEM-BSE image of a polished section of a glass bead from the Dobkowice burial site is shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003eA. Surficial alteration of this sample takes the form of a distinct thin rim surrounding the entire sample. The rim appears to exhibit spalling, which is most likely an artefact created during sample embedding in epoxy. The actual boundary of the spalling is not strictly correlated to the boundary of the alteration rim with the bulk glass. The high-resolution SEM-BSE image in Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003eB shows that the rim is composed of a relatively homogenous ~ 50 µm-thick surficial layer (SL#1) with a sharp interface with the bulk glass interface. There is also a very thin and heterogenous over-layer (SL#2) that represents the topmost part of the alteration rim, and these two layers resemble those in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e. The SEM-EDX map in Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003eC shows that the surficial layer can vary in thickness, here it is on the order of 50–100 µm. The principal alteration layer (SL#1) is depleted in Na and enriched in Si and Al. Figure S1 shows SEM-EDS maps overlaid on SEM-BSE images from a non-polished ‘as-is’ fractured surface from the Dobkowice sample, confirming that SL#1, the layer that is Na-poor and Si and Al-rich is attached to the bulk glass, and that the spalling in Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003e is due to sample preparation. The principal alteration layer shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003eC displays a more complex morphology, as evidenced, for example, by the Al-rich vesicle. It is unclear if the Al-rich vesicle is a result of a glass alteration process, or if it is soil that was incorporated into the surficial layer. This vesicle bears an uncanny resemblance to vesicles seen in oceanic basalt glasses that have been ascribed as being due to microbially-enhanced dissolution.\u003csup\u003e\u003cspan citationid=\"CR81\" class=\"CitationRef\"\u003e81\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe SEM-BSE image in Fig.\u0026nbsp;\u003cspan refid=\"Fig12\" class=\"InternalRef\"\u003e11\u003c/span\u003e reveals a dominant alteration layer (SL#1) with a uniform thickness of approximately 30 µm. There is very little mass-density difference between SL#1 and the bulk glass. The large crack is an epoxy-embedding artefact and should not be confused with the SL#1 interface with the bulk glass. The ToF-SIMS chemical maps in Fig.\u0026nbsp;\u003cspan refid=\"Fig12\" class=\"InternalRef\"\u003e11\u003c/span\u003e chemical maps illustrate that the principal layer (SL#1) is hydrated (as shown in the H + map), enriched in Si, Ca, and just slightly in Mg, and depleted in Na, K, and Al. The principal alteration layer has a very thin external rim (SL#2) characterized by strong Al and K enrichment.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec14\" class=\"Section2\"\u003e \u003ch2\u003eBroborg\u003c/h2\u003e \u003cp\u003eSample BB1b was originally excavated from the Broborg hillfort, as described in the literature.\u003csup\u003e\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e,\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e,\u003cspan citationid=\"CR94\" class=\"CitationRef\"\u003e94\u003c/span\u003e,\u003cspan citationid=\"CR95\" class=\"CitationRef\"\u003e95\u003c/span\u003e\u003c/sup\u003e It was selected for study because it has a significant fraction of glassy material and the surface appeared altered through natural processes.\u003csup\u003e\u003cspan citationid=\"CR94\" class=\"CitationRef\"\u003e94\u003c/span\u003e,\u003cspan citationid=\"CR96\" class=\"CitationRef\"\u003e96\u003c/span\u003e\u003c/sup\u003e Fig.\u0026nbsp;\u003cspan refid=\"Fig13\" class=\"InternalRef\"\u003e12\u003c/span\u003e shows an optical microscopy image and SEM-EDS elemental maps of the sample prepared in cross-section. In Fig.\u0026nbsp;\u003cspan refid=\"Fig13\" class=\"InternalRef\"\u003e12\u003c/span\u003e, the term ‘bulk’ refers to a glassy phase that was created during melting of the protolith rocks and ‘SL’ refers to the surficial layer. The surface of the bulk glass is predominantly mafic, as the mafic glass is two orders of magnitude less viscous than the felsic glass and flowed over the felsic material.\u003csup\u003e\u003cspan citationid=\"CR96\" class=\"CitationRef\"\u003e96\u003c/span\u003e\u003c/sup\u003e Compared to the bulk mafic glass, the surficial layer shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig13\" class=\"InternalRef\"\u003e12\u003c/span\u003eB is enriched in Si and depleted in Na, Al, Mg, Ca, and Fe. The surficial layer in Fig.\u0026nbsp;\u003cspan refid=\"Fig13\" class=\"InternalRef\"\u003e12\u003c/span\u003eC, is also depleted in Na and Fe, and enriched in Si. Ca is depleted, except for certain hotspots with elevated concentrations. The behavior of Mg and Al in the surficial layer is more complex with areas of both enrichment and depletion. The textural and chemical heterogeneity of the bulk glass makes the evaluation of surficial layer formation challenging in samples from the Broborg hillfort.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eSEM-EDS maps of a larger area of the Broborg BB1b sample are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig14\" class=\"InternalRef\"\u003e13\u003c/span\u003e, highlighting the surficial layers associated with the mafic region (individual maps shown in Fig. S2). The alteration layer is highly irregular in morphology and has an approximate average thickness of 14 µm. The chemical composition of the altered layer differs from the amorphous matrix: Si is enriched, Al is depleted, and Fe, Mg, and Na are completely absent, having concentrations below the detection limit (see individual SEM-EDS elemental maps in Fig. S2). Figure\u0026nbsp;\u003cspan refid=\"Fig14\" class=\"InternalRef\"\u003e13\u003c/span\u003e shows the textural and chemical heterogeneity of the bulk glass, with felspar needles, and irregularly shaped iron-bearing pyroxenes and spinels (identified by X-ray diffraction in Matthews et al.\u003csup\u003e\u003cspan citationid=\"CR94\" class=\"CitationRef\"\u003e94\u003c/span\u003e\u003c/sup\u003e) that are present throughout the glassy matrix. These crystalline phases are also present at the interface to such an extent that the glass matrix is rarely in contact with the surficial layer. The aqueous alteration rates of crystalline silicates and spinels are predicted to be significantly slower than silicate glasses. It is uncertain whether alteration of the glass proceeded until the alteration front reached a crystallite, or if these phases crystallized near the surface of the original bulk glass. However, it can be hypothesized that the composition and structure of the underlying matrix had a direct impact on the surficial altered layer.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec15\" class=\"Section2\"\u003e \u003ch2\u003eNewberry\u003c/h2\u003e \u003cp\u003eResults are presented for three samples (MJS-1, BOF-6, and BOF-9) from the Newberry volcano Big Obsidian Flow. Samples BOF-6 and BOF-9 were both excavated in the same approximate vicinity; however, BOF-6 was partially covered in soil while the BOF-9 sample was excavated from one of the walls of the obsidian flow. Sample MJS-1 was taken from the top of the flow. Figure\u0026nbsp;\u003cspan refid=\"Fig16\" class=\"InternalRef\"\u003e14\u003c/span\u003e shows optical and SEM-BSE images of obsidian samples, including photographs taken from near the excavation sites of the three Newberry samples. Visually, the surfaces of MJS-1 and BOF-6 (Figs.\u0026nbsp;\u003cspan refid=\"Fig16\" class=\"InternalRef\"\u003e14\u003c/span\u003eA, E, respectively) both appeared white while the surface layer of BOF-9 had a reddish tint (Fig.\u0026nbsp;\u003cspan refid=\"Fig16\" class=\"InternalRef\"\u003e14\u003c/span\u003eC). However, the BOF-6 surface layer was much more friable, while the surface layer of MJS-1 was consolidated. Both the MJS-1 and BOF-6 samples contained evidence of plant roots present on their surfaces.\u003c/p\u003e \u003cp\u003eThe SEM-EDS elemental maps of sample MJS-1, in Fig.\u0026nbsp;\u003cspan refid=\"Fig16\" class=\"InternalRef\"\u003e14\u003c/span\u003eB, show a relatively non-porous surficial layer that has a variable thickness, ranging from a few µm to ~ 20 µm. In general, this surficial layer was visible along the sample surface that was exposed to the atmosphere. The SEM-EDS chemical map of the BOF-9 sample in Fig.\u0026nbsp;\u003cspan refid=\"Fig16\" class=\"InternalRef\"\u003e14\u003c/span\u003eD shows that the red-colored surficial layer is composed of a highly porous, sponge-like structure that is compositionally similar to the underlying obsidian glass, with a minor fraction of particles, either Fe or Na-rich. The SEM-EDS chemical map of the BOF-6 sample, shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig16\" class=\"InternalRef\"\u003e14\u003c/span\u003eF, reveals a smooth surface that is amply covered with silicon-rich features that are most likely diatoms.\u003csup\u003e\u003cspan citationid=\"CR81\" class=\"CitationRef\"\u003e81\u003c/span\u003e\u003c/sup\u003e At the scale of this image, there is no obvious evidence of an altered layer.\u003c/p\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig17\" class=\"InternalRef\"\u003e15\u003c/span\u003e shows ToF-SIMS ion maps of the altered layer of sample MJS-1. The maps show a ~ 10 µm-thick surficial layer with sharp chemical boundaries at both the inner and outer interfaces. The altered layer appears to be very heterogeneous with respect to its structure and composition, as shown in the SEM-BSE image (Fig.\u0026nbsp;\u003cspan refid=\"Fig17\" class=\"InternalRef\"\u003e15\u003c/span\u003e). This heterogeneity is also reflected in the chemical maps. Na and K are depleted in this layer, while H, Mg, Al, Si, Ca, and Fe are enriched. The depleted and enriched layers are spatially coincident for all elements. The one exception is H, as this element displays two zones: (i) a prominent outer zone of elevated H enrichment is ~ 10 µm thick; and (ii) an adjacent, inner zone ~ 4 µm thick that is characterized by H concentrations just barely above that of the bulk obsidian. Both H zones have relatively sharp boundaries at the scale of the analyses. This contrasts with the H map of the Timna sample (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e), which showed only one very sharp layer of H enrichment.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec16\" class=\"Section2\"\u003e \u003cp\u003e\u003c/p\u003e \u003c/div\u003e "},{"header":"DISCUSSION AND CONCLUSIONS","content":"\u003cp\u003eThe natural and archeological analogues presented here were exposed to different environments for different lengths of time. The analogues were of different chemistry, a parameter that is intimately tied to technological developments, including the ability to melt materials at increasingly higher temperature due to improvements in the high-temperature processing technologies that were employed and the chemistry of the primary material sources used (important for controlling such factors as chemical impurities and oxidation state\u003csup\u003e\u003cspan citationid=\"CR97\" class=\"CitationRef\"\u003e97\u003c/span\u003e\u003c/sup\u003e). The factors of environment, length of time, and chemical composition of the starting material had an influence on the chemistry and morphology of the surface layers and secondary phases that developed in contact with the unaltered bulk glasses. These factors are summarized along with average surficial layer thicknesses in Table\u0026nbsp;\u003cspan refid=\"Tab4\" class=\"InternalRef\"\u003e4\u003c/span\u003e. The use of surficial altered layer thicknesses to compare and estimate rates of glass corrosion should be viewed as very approximate for many reasons. One reason is molar volume changes between the unaltered glass and the phase(s) making up the altered layer. Moreover, the effects of porosity in the altered layer also must be considered. It also cannot be excluded that over time during burial and then retrieval from the soil, some of the surface altered layers may have lost their structural integrity, causing secondary phases to peel or break off, thereby making the altered layers incomplete and thinner.\u003c/p\u003e\u003cp\u003eThe archeological samples described in this study were excavated from near-surface conditions in hydraulically unsaturated environments. This is important as they can be used to support the disposal of LAW glass at the Hanford site IDF. The nominal conditions at the Hanford IDF are an average subterranean temperature of 15°C at a 7.6-m depth with an annual rainfall of 180 mm.\u003csup\u003e\u003cspan citationid=\"CR98\" class=\"CitationRef\"\u003e98\u003c/span\u003e\u003c/sup\u003e After the waste and associated backfill have been placed in the facility, it will be covered with an engineered surface barrier. An infiltration rate of 0.5 mm/year is assumed while this barrier is intact, with the infiltration rate increasing to 3.5 mm/year once the barrier has degraded (after ~ 500 years).\u003csup\u003e\u003cspan citationid=\"CR98\" class=\"CitationRef\"\u003e98\u003c/span\u003e\u003c/sup\u003e Water infiltrating through the backfill will chemically react with the dominant minerals present, which are mostly comprised of silica, as well as some carbonates. The carbonates minerals will lead to buffering of the pore waste to neutral-to-mildly alkaline pH conditions. The IDF temperatures and annual rainfall quantities are closer to those of Timna than the other analogue sites. The glass compositions expected at the IDF are different from the glasses from the analogue sites, having lower Si, Fe, and Al, higher Na, as well as components that are not present in the analogues, including B, Li, V, and Sn. The Ballidon site and other field-testing sites will provide important data on the alteration of compositionally relevant borosilicate glasses in near-surface conditions relevant to the Hanford IDF. Analysis of alteration observed on archeological and modern glasses (including one borosilicate composition) buried at the Ballidon site for 52 years is described in Thorpe et al.\u003csup\u003e\u003cspan citationid=\"CR74\" class=\"CitationRef\"\u003e74\u003c/span\u003e\u003c/sup\u003e Furthermore, analysis of US and UK nuclear waste type glasses buried for 18 and 20 years, respectively, is underway and includes borosilicate, silicate, and Fe-phosphate compositions. An additional test with buried LAW glass samples has also been underway since 2019 and data from those tests will inform glass behavior in the IDF,\u003csup\u003e\u003cspan citationid=\"CR79\" class=\"CitationRef\"\u003e79\u003c/span\u003e\u003c/sup\u003e even though the duration of those tests is much less than that achievable with the archeological glass samples.\u003c/p\u003e\u003cp\u003eThe present work characterizes the surficial alteration features of natural and archeological glasses as a function of the burial environment and the bulk glass composition. The characterizations that were performed confirmed that the samples contained a significant fraction of glassy material. These glassy materials were subjected to alteration under near-surface conditions for periods exceeding 1000 years and fulfil the criteria to be considered as an alteration analogue, since they \u003csup\u003e\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e,\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e,\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u003c/sup\u003e: (i\u003cem\u003e)\u003c/em\u003e are of a known or determinable \u003cb\u003echemistry\u003c/b\u003e (e.g., composition and structure); \u003cem\u003e(ii)\u003c/em\u003e are from a known or determinable \u003cb\u003ealteration environment\u003c/b\u003e (e.g., exposure time, biological contact, solution chemistry, etc.); \u003cem\u003e(iii)\u003c/em\u003e are of a known or determinable \u003cb\u003eprovenance\u003c/b\u003e following its excavation (e.g., storage conditions, sampling history, conservation/restoration, etc.); and \u003cem\u003e(iv)\u003c/em\u003e are measurably \u003cb\u003ealtered.\u003c/b\u003e The physico-chemical characterizations revealed that differences in the chemical composition of the original samples significantly affected their chemical durability. The data in Table\u0026nbsp;\u003cspan refid=\"Tab4\" class=\"InternalRef\"\u003e4\u003c/span\u003e suggest that the average annual air temperature and annual precipitation also have a measurable effect on the observed thickness of the altered surficial layer. Due to the nature of the analogues and their environments (lack of duplicates, different compositions, different temperatures, different rainfall, etc.), it is challenging to isolate the parameter that has a largest effect on surficial layer thickness, and further characterization of samples from additional sites is needed in the future. However, the data show that samples altered in the arid Timna environment have thinner surface layers than samples subjected to greater annual precipitation levels.\u003c/p\u003e\u003cp\u003eIt is important to note that air temperature and average precipitation do not fully parameterize the exposure conditions for these samples, and that future work will investigate the influence of the soil pore water chemistry and the local microbial community on glass alteration. During efforts to characterize and assess the Broborg glasses as alteration analogues, evidence of microbial interaction with the glass surfaces was observed via SEM.\u003csup\u003e\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u003c/sup\u003e Further microscopic and spectroscopic analyses showed glass alteration (chemical and morphological) consistent with microbial activity, evidenced by surficial pitting beneath microbes, suggesting a microbial component to glass corrosion.\u003csup\u003e\u003cspan citationid=\"CR99\" class=\"CitationRef\"\u003e99\u003c/span\u003e\u003c/sup\u003e Bacterial and fungal communities can colonize a variety of natural and synthetic materials, including rock and glass, by forming complex biofilms on the surfaces.\u003csup\u003e\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e\u003c/sup\u003e These microbial biofilms are known to weather these material surfaces using biophysical and biochemical processes (such as penetrating within cracks, producing extracellular polysaccharides, and secreting organic acids).\u003csup\u003e\u003cspan citationid=\"CR100\" class=\"CitationRef\"\u003e100\u003c/span\u003e\u003c/sup\u003e Decades of research have established that microbial communities can persist and even thrive in harsh and toxic environments, suggesting the potential for biotic processes to influence the alteration of vitrified low-level nuclear waste after storage in near-surface geological facilities.\u003csup\u003e\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e,\u003cspan citationid=\"CR99\" class=\"CitationRef\"\u003e99\u003c/span\u003e,\u003cspan citationid=\"CR101\" class=\"CitationRef\"\u003e101\u003c/span\u003e,\u003cspan citationid=\"CR102\" class=\"CitationRef\"\u003e102\u003c/span\u003e\u003c/sup\u003e However, most studies evaluating the long-term durability of vitrified nuclear waste glass have focused on the abiotic degradation of these materials in sterile environments.\u003csup\u003e\u003cspan citationid=\"CR100\" class=\"CitationRef\"\u003e100\u003c/span\u003e\u003c/sup\u003e While the presence of microbes in these geological facilities is recognized,\u003csup\u003e\u003cspan citationid=\"CR103\" class=\"CitationRef\"\u003e103\u003c/span\u003e,\u003cspan citationid=\"CR104\" class=\"CitationRef\"\u003e104\u003c/span\u003e\u003c/sup\u003e only a few studies have attempted to characterize and extrapolate the observed short-term microbial impacts to predict the long-term (i.e., thousands of years) bio-alteration of vitrified nuclear waste, and this is an ongoing area of research.\u003csup\u003e\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e,\u003cspan citationid=\"CR100\" class=\"CitationRef\"\u003e100\u003c/span\u003e,\u003cspan citationid=\"CR105\" class=\"CitationRef\"\u003e105\u003c/span\u003e,\u003cspan citationid=\"CR106\" class=\"CitationRef\"\u003e106\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\u003cp\u003eTo conclude, the knowledge obtained on how different environmental factors influence the alteration of vitrified archeological samples can be applied to vitrified nuclear waste materials. The subsequent incorporation of these factors into performance assessment models will allow for the development a more holistic long-term prediction of the vitrified material durability under field conditions.\u003c/p\u003e\u003cp\u003e \u003c/p\u003e\u003cdiv class=\"gridtable\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e\u003ctable float=\"Yes\" id=\"Tab4\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 4\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eSummary of analogue glass site data\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e\u003ccolgroup cols=\"7\"\u003e\u003c/colgroup\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSite and sample\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eAverage SEM surficial layer thickness, µm\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eAverage air temperature and annual precipitation\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eSample age\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eDescription of chemical and mineralogical makeup\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eAnalogue Advantages\u003c/p\u003e \u003c/th\u003e\u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eAnalogue Limitations\u003c/p\u003e \u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eTimna Tuyère\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2 ± 0.2\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e15°C, 25 mm annual rainfall. Arid with periodic floods\u003csup\u003e\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e3150 ± 50 yrs\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eCopper slag (iron-rich glass with fayalite and copper-rich inclusions)\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003eVarious alteration timescales, arid, amorphous, known provenance, near surface\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eOpen system, heterogeneous, more arid than IDF, limited alteration\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eBroborg-BB1b\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e8 ± 2 (felsic glass), 13 ± 10 (mafic glass)\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e5°C, 572 mm annual rainfall\u003csup\u003e\u003cspan citationid=\"CR94\" class=\"CitationRef\"\u003e94\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1500 yrs\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eEither mafic-derived glass + spinel + pyroxene or felsic-derived glass + quartz + feldspar\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003eDifference glass chemistries, known provenance, near surface\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eHeterogeneous, challenging surface analyses, more rain than IDF\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eBallidon\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eVariable depending on sample (\u0026gt; 400 µm for replica medieval glass)\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e9–10°C, 908 mm annual rainfall\u003csup\u003e\u003cspan citationid=\"CR107\" class=\"CitationRef\"\u003e107\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e18–52 yrs\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eSilicate, borosilicate, lead-silicate and Fe-phosphate compositions (US, UK and Russian nuclear waste glass)\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003eDifferent glass chemistries, controlled experiment, high rainfall, near surface\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eShort alteration timescale, cooler and more rain than IDF\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eNewberry-MJS-1\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e8.65 ± 5.24\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0°C, 635 mm annual rainfall\u003csup\u003e\u003cspan citationid=\"CR108\" class=\"CitationRef\"\u003e108\u003c/span\u003e,\u003cspan citationid=\"CR109\" class=\"CitationRef\"\u003e109\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1350 yrs (most recent lava flow)\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eObsidian\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003eHomogeneous, natural, known provenance\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eNot buried, only one glass chemistry\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDobkowice\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e59 ± 2\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0°C, 700 mm annual rainfall\u003csup\u003e\u003cspan citationid=\"CR110\" class=\"CitationRef\"\u003e110\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e2600 yrs\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eSoda-lime-silica glass\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003eVarious alteration timescales, arid, amorphous, known provenance, near surface\u003c/p\u003e \u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eOpen system, heterogeneous, more arid than IDF, limited alteration\u003c/p\u003e \u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/table\u003e\u003c/div\u003e"},{"header":"METHODS","content":"\u003cp\u003eOne of the main goals of the present study is to provide a general physical and chemical characterization of glass analogs recovered from the five sites. The techniques used provide information at various scales, with a maximum of micrometer-spatial resolution. Future work will involve techniques that have much higher spatial and mass resolution, such as transmission electron microscopy (TEM), atom probe tomography (APT), TEM-tomography, nano secondary ion mass spectrometry (nanoSIMS), etc. to characterize the altered samples. Such high-resolution analysis techniques have been shown to provide significant insights into the interfacial region that delimit the boundary between the non-altered parent material and overlying authigenic surface layers (SL). Atomic scale measurements are crucial for future interpretation of the mechanisms of alteration.\u003csup\u003e\u003cspan additionalcitationids=\"CR81 CR82\" citationid=\"CR80\" class=\"CitationRef\"\u003e80\u003c/span\u003e–\u003cspan citationid=\"CR83\" class=\"CitationRef\"\u003e83\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e\u003ch2\u003eOptical microscopy, scanning electron microscopy (SEM), and electron probe microanalysis (EPMA)\u003c/h2\u003e\u003cp\u003eOptical microscopy was performed with a Keyence VHX 7000 optical microscope. Samples were observed either ‘as received’, to evaluate surficial layers prior to any additional sample preparation involving exposure to water, or as polished sections for more detailed characterization of the chemistry and morphology. Polished sections were made by first fracturing bulk material, embedding grains in epoxy, and then polishing sequentially with 240, 320, 400, 600, 800, and 1200 grit SiC abrasive paper in the presence of water (exposure to water during polishing is on the order of minutes compared to the hundreds of years the archeological samples have been in contact with water and should have a negligible impact on alteration layer thickness and morphology). This was followed by polishing with a 1-µm diamond paste suspension. Much higher spatial resolution imaging of polished sections was performed using a JEOL 7001F SEM operated with a 15 kV accelerating voltage and 13 nA probe current. Energy-dispersive spectroscopy (EDS) analyses were performed with a Bruker Xflash 6 60 X-ray detector with a spectral resolution of 129 eV. Energy-dispersive X-ray spectra were processed using Bruker Esprit v2.1 software. Higher accuracy chemical composition measurements were made by electron probe microanalysis (EPMA) using a JEOL 8530 instrument operated with a 15 kV accelerating voltage and 20 nA probe current. Wavelength-dispersive spectroscopic (WDS) measurements were made with five spectrometers for high-energy resolution compositional measurements and analysis of light elements.\u003c/p\u003e\u003ch2\u003eX-ray computed tomography\u003c/h2\u003e\u003cp\u003eThe internal 3-D microstructure of the samples was analyzed using X-ray micro computed tomography (micro-CT) using a Thermo Fisher Scientific Heliscan Micro-CT system. Samples were mounted on Styrofoam and scanned with an 80 kV \u003cem\u003ep\u003c/em\u003e unfiltered microfocus X-ray source with a \u0026lt; 1.5 µm diameter focal spot. Projections were acquired in a space-filling trajectory with a detector shift applied to help lessen the impact of pixel-specific artifacts. The acquired projections were reconstructed on a GPU cluster using iterative methods, yielding digital 3D volumes with voxel sizes around 5 µm\u003csup\u003e\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003e. Image segmentation was performed on the X-ray projections to partition the projections into: (i) bulk phase of the samples (assumed to be the amorphous phase); (ii) bright inclusions (assumed to be crystals); (iii) voids; and (iv) background. The segmented projects were then stitched together to form a reconstructed 3-dimensional representation of the samples and the voxels corresponding to the amorphous phase were summed and normalized to the total volume of the amorphous and crystalline phases.\u003c/p\u003e\u003ch2\u003eX-ray diffraction (XRD)\u003c/h2\u003e\u003cp\u003eXRD was performed with a Bruker Advance D8 X-ray diffractometer using a Cu \u003cem\u003eK\u003c/em\u003eα X-ray source operated at 40 kV and 40 mA. Samples were either in bulk form or fine powders that were produced using a tungsten carbide mill. For semi-quantitative amorphous fraction analysis, sample powders were mixed with a 5 wt.% CeO\u003csub\u003e2\u003c/sub\u003e internal standard. XRD scans were collected from 5–70° 2θ with a step size of 0.015° and a dwell time of 30 s. Phase identification of XRD patterns was carried out with EVA 4.0 using the PDF4 + database from the Inorganic Crystal Structure Database (ICSD). Rietveld refinement was used for semi-quantitative analyses of the amorphous sample fractions with TOPAS 4.0 software.\u003c/p\u003e\u003ch2\u003eTime of flight secondary ion mass spectroscopy (ToF-SIMS)\u003c/h2\u003e\u003cp\u003eToF-SIMS measurements were performed using a ToF.SIMS5 instrument (IONTOF GmbH, Münster, Germany). ToF-SIMS has many advantages of SEM-EDS, including improved elemental detection limits and the ability to measure hydrogen (H). The distribution of H in the alteration layer of polished analogue samples was measured using experimental conditions optimized for high signal-to-noise (S/N) ratios of H.\u003csup\u003e\u003cspan citationid=\"CR84\" class=\"CitationRef\"\u003e84\u003c/span\u003e\u003c/sup\u003e A 25.0 keV Bi\u003csup\u003e+\u003c/sup\u003e beam was used as the analysis beam to collect positive secondary ion maps of the following ions: H\u003csup\u003e+\u003c/sup\u003e, Li\u003csup\u003e+\u003c/sup\u003e, Na\u003csup\u003e+\u003c/sup\u003e, Ca\u003csup\u003e++\u003c/sup\u003e, Ca\u003csup\u003e+\u003c/sup\u003e, Si\u003csup\u003e+\u003c/sup\u003e, \u003csup\u003e30\u003c/sup\u003eSi\u003csup\u003e+\u003c/sup\u003e, Al\u003csup\u003e+\u003c/sup\u003e, Mg\u003csup\u003e+\u003c/sup\u003e, C\u003csup\u003e+\u003c/sup\u003e, K\u003csup\u003e+\u003c/sup\u003e, Cu\u003csup\u003e+\u003c/sup\u003e, and \u003csup\u003e54\u003c/sup\u003eFe\u003csup\u003e+\u003c/sup\u003e. A 1.0 keV O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e+\u003c/sup\u003e sputter beam with 240 nA current was used before and during analysis to remove surface contamination and control the hydrogen background. The O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e+\u003c/sup\u003e beam was scanned over a 700×700 µm\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e area for 600 s before data collection to remove surface contamination. During collection of ion maps, the instrument was operated in a non-interlaced mode. The Bi\u003csup\u003e+\u003c/sup\u003e beam was focused to a 400 nm diameter with a beam current of 1.70 pA at 20 kHz frequency. Maps were acquired over 200×200 µm\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e, 150×150 µm\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e, or 50×50 µm\u003csup\u003e\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e areas with 256×256 pixels. During non-interlaced mode imaging collection, each cycle was composed of three steps: (i) the O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e+\u003c/sup\u003e beam was scanned over the sample for 1 s to remove H adsorbed on the surface to control the H background, (ii) a 0.5 s pulse was used for charging control so that reasonable signal intensity could be achieved, (iii) 2 scans for ion map collection, with 256×256 pixels per scan. 50–200 scan cycles were accumulated during data collection.\u003c/p\u003e\u003ch2\u003eChemical digestion and elemental analysis\u003c/h2\u003e\u003cp\u003eChemical digestion was carried out by microwave assisted acid digestion. Inductively coupled plasma-optical emission spectroscopy (ICP-OES) analysis was performed on an Agilent 5110 VDV (Agilent Technologies, Santa Clara, CA) for major elements. Inductively coupled plasma-mass spectrometry (ICP-MS) was performed with a Perkin Elmer model NexION 2000B for trace elements (i.e., Cr and Zr). The chemical digestion procedure and subsequent elemental analyses were performed following test protocol USEPA3052B.\u003csup\u003e\u003cspan citationid=\"CR85\" class=\"CitationRef\"\u003e85\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eJ.M., J.C., J.N., C.P., R.G., R.H., C.T., E.B., J.M., D.K., R.H., R.S., and A.K. wrote main manuscript text. Z.Z. performed ToF-SIMS measurements. A.D. and S.L. performed XCT measurements. L.B., E.G., O.Y., E.B., and D.K. provided Timna samples and wrote sections related to Timna. R.H. and C.T. provided data for Ballidon and wrote Ballidon section. R.G., J.C., P.N., and M.S., provided Dobkowice samples. M.J. provided Newberry samples and project guidance. S.C., J.H., A.P., N.B., R.A., and A.K. performed laboratory measurements. All authors reviewed the manuscript\u003c/p\u003e\u003ch2\u003eAcknowledgement\u003c/h2\u003e\u003cp\u003eThis work is supported by the Waste Treatment and Immobilization Plant Project at the United States Department of Energy (US DOE) Hanford Field Office (HFO). The authors gratefully acknowledge Professor Peter Kresten for supplying the original vitrified samples from Broborg and Professor Sylwester Czopek for help with archeologic data of the Dobkowice sample. A portion of the research was performed using the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE\u0026rsquo;s Office of Biological and Environmental Research located at Pacific Northwest National Laboratory under proposal number 60748 (Award DOI: 10.46936/lsr.proj.2023.60748/60008973). Pacific Northwest National Laboratory is operated for the DOE by Battelle Memorial Institute under Contract DE-AC06\u0026ndash;76RLO 1830.\u003c/p\u003e\u003ch2\u003eData Availability\u003c/h2\u003e\u003cp\u003eData sets generated during the current study are available from the corresponding author on reasonable request.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eCrovisier, J.-L., Advocat, T. \u0026amp; Dussossoy, J.-L. Nature and role of natural alteration gels formed on the surface of ancient volcanic glasses (Natural analogs of waste containment glasses). Journal of Nuclear Materials 321, 91\u0026ndash;109, (2003).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eTecher, I. \u003cem\u003eet al.\u003c/em\u003e Alteration of a basaltic glass in an argillaceous medium: The Salagou dike of the Lod\u0026egrave;ve Permian Basin (France). Analogy with an underground nuclear waste repository. Geochimica et Cosmochimica Acta 65, 1071\u0026ndash;1086, (2001).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMiller, W. \u003cem\u003eet al.\u003c/em\u003e Natural Analogue Studies in the Geological Disposal of Radioactive Wastes. Report No. DOE-HMIP-RR\u0026ndash;94031, (United Kingdom, 1994).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLutze, W. \u003cem\u003eet al.\u003c/em\u003e Alteration of basalt glasses: implications for modelling the long-term stability of nuclear waste glasses. Nature 314, 252\u0026ndash;255, (1985).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eEwing, R. C. Natural glasses: analogues for radioactive waste forms. \u003cem\u003eMaterials Research Society Symposium Proceedings\u003c/em\u003e 1, 57\u0026ndash;68, (1979).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eTecher, I., Advocat, T., Lancelot, J. \u0026amp; Liotard, J. M. Basaltic glass: alteration mechanisms and analogy with nuclear waste glasses. Journal of Nuclear Materials 282, 40\u0026ndash;46, (2000).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMalow, G. \u0026amp; Lutze, W. Alteration Effects and Leach Rates of Basaltic Glasses: Implications for the Long-Term Stability of Nuclear Waste Form Borosilcate Glasses. Journal of Non-Crystalline Solids 67, 305\u0026ndash;321, (1984).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLibourel, G. The use of natural and archeological analogues for understanding the long-term behavior of nuclear glasses. Comptes Rendus Geosci. 343, (2011).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eEwing, R. C. \u0026amp; Roed, G. Natural analogues: Their application to the prediction of the long-term behavior of nuclear waste glasses. \u003cem\u003eMaterials Research Society Symposium Proceedings\u003c/em\u003e 84, 67\u0026ndash;83, (1987).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMichelin, A. \u003cem\u003eet al.\u003c/em\u003e Effect of iron metal and siderite on the durability of simulated archeological glassy material. Corrosion Science 76, 403\u0026ndash;414, (2013).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eRyan, J. \u003cem\u003eet al.\u003c/em\u003e Ancient Roman Glass Characterization for use in Glass Corrosion Modeling. Report No. PNNL-21847, (Pacific Northwest National Laboratory, Richland, WA, USA, 2012).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eVerney-Carron, A., Gin, S. \u0026amp; Libourel, G. A fractured roman glass block altered for 1800 years in seawater: Analogy with nuclear waste glass in a deep geological repository. Geochimica et Cosmochimica Acta 72, 5372\u0026ndash;5385, (2008).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eVerney-Carron, A., Gin, S., Frugier, P. \u0026amp; Libourel, G. Long-term modeling of alteration-transport coupling: Application to a fractured Roman glass. Geochimica Et Cosmochimica Acta 74, 2291\u0026ndash;2315, (2010).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eVerney-Carron, A., Gin, S. \u0026amp; Libourel, G. Archaeological analogs and the future of nuclear waste glass. Journal of Nuclear Materials 406, 365\u0026ndash;370, (2010).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eNava-Farias, L. \u003cem\u003eet al.\u003c/em\u003e Applying laboratory methods for durability assessment of vitrified material to archaeological samples. npj Materials Degradation 5, 57, (2021).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eTecher, I., Advocat, T., Lancelot, J. \u0026amp; Liotard, J. M. Dissolution kinetics of basaltic glasses: control by solution chemistry and protective effect of the alteration film. Chemical Geology 176, 235\u0026ndash;263, (2001).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eZanini, R., Franceschin, G., Cattaruzza, E. \u0026amp; Traviglia, A. A review of glass corrosion: the unique contribution of studying ancient glass to validate glass alteration models. npj Materials Degradation 7, 38, (2023).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWeaver, J. L. \u003cem\u003eet al.\u003c/em\u003e Pre-viking Swedish hillfort glass: A prospective long-term alteration analogue for vitrified nuclear waste. International Journal of Applied Glass Science 9, 540\u0026ndash;554, (2018).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSilvestri, A. The coloured glass of Iulia Felix. Journal of Archaeological Science 35, 1489\u0026ndash;1501, (2008).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSilvestri, A., Molin, G. \u0026amp; Salviulo, G. The colourless glass of Iulia Felix. Journal of Archaeological Science 35, 331\u0026ndash;341, (2008).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSilvestri, A., Molin, G. \u0026amp; Salviulo, G. Archaeological glass alteration products in marine and land-based environments: morphological, chemical and microtextural characterization. Journal of Non-Crystalline Solids 351, 1338\u0026ndash;1349, (2005).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eGeisler, T. \u003cem\u003eet al.\u003c/em\u003e Aqueous corrosion of borosilicate glass under acidic conditions: A new corrosion mechanism. Journal of Non-Crystalline Solids 356, 1458\u0026ndash;1465, (2010).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSchalm, O., Nuyts, G. \u0026amp; Janssens, K. Some critical observations about the degradation of glass: The formation of lamellae explained. Journal of Non-Crystalline Solids 569, (2021).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLibourel, G. \u003cem\u003eet al.\u003c/em\u003e The use of natural and archeological analogues for understanding the long-term behavior of nuclear glasses. Comptes Rendus Geoscience 343, 237\u0026ndash;245, (2011).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWeaver, J., MccLoy, J., Ryan, J. V. \u0026amp; Kruger, A. A. Ensuring longevity: Ancient glasses help predict durability of vitrified nuclear waste. American Ceramic Society Bulletin 95, 18\u0026ndash;23, (2016).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSj\u0026ouml;blom, R. \u003cem\u003eet al.\u003c/em\u003e Assessment of the reason for the vitrification of a wall at a hillfort. The example of Broborg in Sweden. Journal of Archaeological Science: Reports 43, 103459, (2022).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePlymale, A. E. \u003cem\u003eet al.\u003c/em\u003e Niche Partitioning of Microbial Communities at an Ancient Vitrified Hillfort: Implications for Vitrified Radioactive Waste Disposal. Geomicrobiology Journal 38, 1\u0026ndash;21, (2020).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eEnglund, M. \u003cem\u003eet al.\u003c/em\u003e Broborg Hillfort: A Research Study of the Vitrified Wall. The Archaeologists. Report No. 2018:103, (National Historical Museums, Stockholm, Sweden, 2018).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eOgenhall, E. Amphibolitic rocks near Broborg, Uppland. Chemical and mineralogical analyses of metamorphic mafic-intermediate rocks from outcrops near the prehistoric vitrified Hhllfort Broborg and a boulder in the hillfort. Report No. RA\u0026Auml; 156:1, (Arkeologerna, Uppland, Sweden, 2016).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKresten, P. \u0026amp; Ambrosiani, B. Swedish vitrified forts: a reconnaissance study. Fornv\u0026auml;nnen Journal of swedish antiquarian research 87, 1\u0026ndash;17, (1992).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMcCloy, J. S. \u003cem\u003eet al.\u003c/em\u003e Reproduction of melting behavior for vitrified hillforts based on amphibolite, granite, and basalt lithologies. Scientific Reports 11, 1272, (2021).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSj\u0026ouml;str\u0026ouml;m, J. K. \u003cem\u003eet al.\u003c/em\u003e Late Holocene peat paleodust deposition in south-western Sweden-exploring geochemical properties, local mineral sources and regional aeolian activity. Chemical Geology 602, 120881, (2022).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSwedish University of Agricultural Sciences (SLU). \u003cem\u003eDigital soil map of Sweden\u003c/em\u003e, \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003e\u0026lt;https://gis-slu.maps.arcgis.com/apps/StorytellingSwipe/index.html?appid=e55d28b98d\u003c/span\u003e\u003cspan address=\"http://%3Chttps://gis-slu.maps.arcgis.com/apps/StorytellingSwipe/index.html?appid=e55d28b98d\" targettype=\"URL\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e2241e0a6c91ae42073b52f\u0026gt; (2017).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLjungqvist, F. C. A new reconstruction of temperature variability in the extra-tropical Northern Hemisphere during the last two millennia. Geografiska Annaler: Series A, Physical Geography 92, 339\u0026ndash;351, (2010).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eGibbons, A. \u003cem\u003eWhy 536 was \u0026lsquo;the worst year to be alive'\u003c/em\u003e, \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003e\u0026lt;https://www.science.org/content/article/why-536-was-worst-year-be-alive\u0026gt;\u003c/span\u003e\u003cspan address=\"http://%3Chttps://www.science.org/content/article/why-536-was-worst-year-be-alive%3E\" targettype=\"URL\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e (2018).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eAmundsen, B. \u0026amp; Baxilchuk, N. The long harsh Fimbul Winter is not a myth. Science Norway 24, (2019).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMoberg, A. \u003cem\u003eet al.\u003c/em\u003e Highly variable Northern Hemisphere temperatures reconstructed from low-and high-resolution proxy data. Nature 433, 613\u0026ndash;617, (2005).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eIlani, S., Flexer, A. \u0026amp; Kronfeld, J. Copper mineralization in sedimentary cover associated with tectonic elements and volcanism in Israel. Mineralium Deposita 22, (1987).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBen-Yosef, E. Back to Solomon's era: results of the first excavations at \u0026ldquo;Slaves' Hill\u0026rdquo;(site 34, Timna, Israel). Bulletin of the American Schools of Oriental Research 376, 169\u0026ndash;198, (2016).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWestern, S. The Classificaiton of Arid Zone Soils. Journal of Soil Science 23, 279\u0026ndash;297, (1972).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eDan, J., Yaalon, D., Moshe, R. \u0026amp; Nissim, S. Evolution of Reg soils in southern Israel and Sinai. Geoderma 28, 173\u0026ndash;202, (1982).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eRavikovitch, S. Soil Map of Southern Israel (Hebrew University of Jerusalem Soil and Water Sciences, 1924).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eDan, Y., Raz, Z., Yaalon, H. \u0026amp; Koyumdjisky, H. Soil Map of Isra\u0026euml;l. (Survey of Israel, 1975).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eInternational Union of Soil Science (IUSS). World Reference Base for Soil Resources. IUSS Working Group WRB, (2015).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eCavanagh, M., Ben-Yosef, E. \u0026amp; Langgut, D. Fuel exploitation and environmental degradation at the Iron Age copper industry of the Timna Valley, southern Israel.. Scientific Reports 12, 15434, (2022).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eRosen, S. A. Basic instabilities? Climate and culture in the Negev over the long term. Geomorphology 32, 6\u0026ndash;22, (2017).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBruins, H. J. Ancient desert agriculture in the Negev and climate-zone boundary changes during average, wet and drought years: Ancient Agriculture in the Middle East. Journal of Arid Environments 86, 28\u0026ndash;42, (2012).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eAlpert, P. \u003cem\u003eet al.\u003c/em\u003e Climatic trends to extremes employing regional modeling and statistical interpretation over the E. Mediterranean. Global and Planetary Change 63, 163\u0026ndash;170, (2008).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLinneman, S. R. \u0026amp; Myers, J. D. Magmatic inclusions in the Holocene rhyolites of Newberry Volcano, central Oregon. Journal of Geophysical Research: Solid Earth 95, 17677\u0026ndash;17691, (1990).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMacLeod, N. S. \u0026amp; Sammel, E. Newberry Volcano, Oregon: a cascade range geothermal prospect. Oregon Geology 44, 123\u0026ndash;131, (1982).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHildreth, W. Quaternary magmatism in the Cascades - Geologic perspectives. US Geological Survey Professional Paper, 1-125, (2007).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJensen, R. A., Donnelly-Nolan, J. M. \u0026amp; Mckay, D. \u003cem\u003eA field guide to Newberry Volcano, Oregon\u003c/em\u003e. The Geological Society of America Field Guide 15 edn, (2009).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLinneman, S. R., \u0026amp; Myers, J. D.. Magmatic inclusions in the Holocene rhyolites of Newberry volcano, central Oregon. Journal of Geophysical Research: Solid Earth 95, 17677\u0026ndash;17691, (1990).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eUSDA. \u003cem\u003eSoil Survey Staff, Natural Resources Conservation Service\u003c/em\u003e, \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003e\u0026lt;https://www.nrcs.usda.gov/resources/data-and-reports/web-soil-survey\u0026gt;\u003c/span\u003e\u003cspan address=\"http://%3Chttps://www.nrcs.usda.gov/resources/data-and-reports/web-soil-survey%3E\" targettype=\"URL\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e (2024).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMann, M. E., Zhang, Z., Hughes, M. K., Bradley, R. S., Miller, S. K., Rutherford, S., \u0026amp; Ni, F.. Global signatures and dynamical origins of the Little Ice Age and Medieval Climate Anomaly. Science 326, 1256\u0026ndash;1260, (2009).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eGedalof, Z. e., Mantua, N. J. \u0026amp; Peterson, D. L. A multi-century perspective of variability in the Pacific Decadal Oscillation: new insights from tree rings and coral. Geophysical Research Letters 29, (2002).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMote, P. W., Hamlet, A. F., Clark, M. P., \u0026amp; Lettenmaier, D. P.. Declining mountain snowpack in western North America. Bulletin of the American Meteorological Society 86, 39\u0026ndash;49, (2005).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eGolovchak, R. \u003cem\u003eet al.\u003c/em\u003e Remedial insight on ageing of glass through the study of ancient man-made artefacts. Archaeometry 63, 312\u0026ndash;326, (2021).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eAngelini, I., Gratuze, B. \u0026amp; Artioli, G. in \u003cem\u003eThe Contribution of Mineralogy to Cultural Heritage\u003c/em\u003e (eds G. Artioli \u0026amp; R. Oberti) Glass and other vitreous materials through history 87\u0026ndash;150 (Mineralogical Society, 2019).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eFurmanek, W. Antropoinfosfera wsp\u0026oacute;łczesnego człowieka. Dydaktyka informatyki 8, 49\u0026ndash;73, (2013).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eFurmanek, M. \u003cem\u003eet al.\u003c/em\u003e Dobkowice revisited. Interdisciplinary research on an enclosure of the Jordan\u0026oacute;w culture. Anthropologie. International Journal of Human Diversity and Evolution 51, 375\u0026ndash;396, (2014).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKuznicki, F. \u003cem\u003eSoil Map of Poland [1:2,000,000]\u003c/em\u003e, \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003e\u0026lt;https://esdac.jrc.ec.europa.eu/images/Eudasm/PL/pol_x6.jpg\u0026gt;\u003c/span\u003e\u003cspan address=\"http://%3Chttps://esdac.jrc.ec.europa.eu/images/Eudasm/PL/pol_x6.jpg%3E\" targettype=\"URL\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e (1984).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLamb, H. Climatic changes in our own times and future threats. Geography, 203\u0026ndash;220, (1982).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePerșoiu, A. \u003cem\u003eet al.\u003c/em\u003e Holocene winter climate variability in Central and Eastern Europe. Scientific Reports 7, 1\u0026ndash;8, (2017).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBr\u0026aacute;zdil, R. \u003cem\u003eet al.\u003c/em\u003e Historical climatology in Europe\u0026ndash;the state of the art. Climatic Change 70, 363\u0026ndash;430, (2005).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePrzybylak, R. Recent air-temperature changes in the Arctic. Annals of Glaciology 46, 316\u0026ndash;324, (2007).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eDomonkos, P. \u003cem\u003eet al.\u003c/em\u003e Variability of extreme temperature events in south\u0026ndash;central Europe during the 20th century and its relationship with large-scale circulation. International Journal of Climatology: A Journal of the Royal Meteorological Society 23, 987\u0026ndash;1010, (2003).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHand, R. J. The Ballidon glass burial experiment \u0026ndash;\u0026thinsp;35 years on. Glass Technology 46, 237\u0026ndash;242, (2005).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMcLoughlin, S. \u003cem\u003eet al.\u003c/em\u003e The long term corrosion of glasses: analytical results after 32 years of burial at Ballidon. Glass Technology-European Journal of Glass Science and Technology Part A 47, 59\u0026ndash;67, (2006).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eNamboodri Jr, C. \u0026amp; Wicks, G. SRL in-situ tests in the United Kingdom: Part 2, Surface analyses of SRS waste glass buried for one and two years in limestone at Ballidon, UK. Report No. WSRC-TP-91-288, (Savannah River Site, Aiken, SC, USA, 1991).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eUnited Kingdom Meteorlogical Office. \u003cem\u003eUK Climate Averages for Nottingham\u003c/em\u003e, \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003e\u0026lt;https://www.metoffice.gov.uk/research/climate/maps-and-data/uk-climate-averages\u0026gt;\u003c/span\u003e\u003cspan address=\"http://%3Chttps://www.metoffice.gov.uk/research/climate/maps-and-data/uk-climate-averages%3E\" targettype=\"URL\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e (2024).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eUnited Kingdom Soil Observatory (UKSO). \u003cem\u003eSoil Map of Derbyshire\u003c/em\u003e, \u0026lt;\u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://mapapps2.bgs.ac.uk/ukso/home.html\u0026gt;\u003c/span\u003e\u003cspan address=\"https://mapapps2.bgs.ac.uk/ukso/home.html%3E\" targettype=\"URL\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e (2024).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHallett, S. H., Sakrabani, R., Keay, C. A. \u0026amp; Hannam, J. A. Developments in land information systems: examples demonstrating land resource management capabilities and options. Soil Use and Management 33, 514\u0026ndash;529, (2017).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eThorpe, C. \u003cem\u003eet al.\u003c/em\u003e Insights into long-term glass corrosion mechanismsfrom the Ballidon project: a 50-year-old glass burialexperiment in an alkaline near surface environment. NPJ Materials Degradation, under review, (2024).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eJantzen, C. M. \u003cem\u003eet al.\u003c/em\u003e Performance of a buried radioactive high level waste (HLW) glass after 24 years. Journal of Nuclear Materials 378, 244\u0026ndash;256, (2008).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWicks, G. G. US field testing programs and results. Journal of Nuclear Materials 298, 78\u0026ndash;85, (2001).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWeart, W. D. Evaluation of salt beds in New Mexico as a geologic repository for nuclear waste. [Waste Isolation Pilot Plant (WIPP)]. Report No. SAND-78-2086C, (Sandia Laboratory, Alburquerque, NM, USA, 1978).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBacon, D. \u003cem\u003eet al.\u003c/em\u003e Field-Scale Lysimeter Studies of Low-Activity Waste Form Degradation. Report No. PNNL-27394, (Pacific Northwest National Laboratory, Richland, WA, USA, 2018).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eNeeway, J. J. \u003cem\u003eet al.\u003c/em\u003e Review of intermediate-scale field tests in support of disposal of waste forms. Chemosphere 347, 140625, (2024).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eGeisler, T. \u003cem\u003eet al.\u003c/em\u003e The mechanism of borosilicate glass corrosion revisited. Geochimica et Cosmochimica Acta 158, 112\u0026ndash;129, (2015).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHellmann, R. in \u003cem\u003eEncyclopedia of Glass Science, Technology, History, and Culture, Vol II\u003c/em\u003e (ed P. Richet) Corrosion of natural glasses in seawater 831\u0026ndash;842 (The American Ceramic Society, 2021).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHellmann, R. in \u003cem\u003eEncyclopedia of Glass Science, Technology, History, and Culture, Vol I\u003c/em\u003e (ed P. Richet) Mechanisms of glass corrosion by aqueous solutions 647\u0026ndash;662 (The American Ceramic Society, 2021).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHellmann, R. \u003cem\u003eet al.\u003c/em\u003e Nanometre-scale evidence for interfacial dissolution-reprecipitation control of silicate glass corrosion. Nature Materials 14, 307\u0026ndash;311, (2015).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePaudel, B. \u003cem\u003eet al.\u003c/em\u003e ToF-SIMS in material research: A view from nanoscale hydrogen detection. Materials Today 75, 149\u0026ndash;165, (2024).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eEPA \u0026ndash; U.S. Environmental Protection Agency. SW-846 Test Method 3052: Microwave Assisted Acid Digestion of Siliceous and Organically Based Matrices. (U.S. Environmental Protection Agency, Washington, D.C, 1996).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eFletcher, W. The chemical durability of glass. A burial experiment at Ballidon in Derbyshire. Journal of Glass Studies, 149\u0026ndash;151, (1972).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBen-Yosef, E. \u0026amp; Rothenberg, B. \u003cem\u003eMining for ancient copper: Essays in memory of Beno Rothenberg\u003c/em\u003e. (Eisenbrauns, 2018).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHauptmann, A. \u003cem\u003eArchaeometallurgy-Materials Science Aspects\u003c/em\u003e. (Springer, 2020).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eAvner, U. \u003cem\u003eet al.\u003c/em\u003e Ancient copper mines at Nahal Amram, southern Arabah. \u003cem\u003eMining for Ancient Copper\u0026ndash;Essays in Memory of Beno Rothenberg\u003c/em\u003e, 147\u0026ndash;177, (2018).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eRothenberg, B. Ancient copper industries in the western Arabah: an archaeological survey of the Arabah, Part 1. Palestine Exploration Quarterly 94, 5\u0026ndash;71, (1962).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eRothenberg, B. Archaeo-metallurgical researches in the southern Arabah 1959\u0026ndash;1990. Part I: Late Pottery Neolithic to Early Bronze IV. Palestine Exploration Quarterly 131, 68\u0026ndash;89, (1999).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBarbana, F., Bertoncello, R., Milanese, L. \u0026amp; Sada, C. Alteration and corrosion phenomena in Roman submerged glass fragments. Journal of Non-Crystalline Solids 337, 136\u0026ndash;141, (2004).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLonginelli, A., Silvestri, A., Molin, G. \u0026amp; Salviulo, G. 1.8 ka old glass from the Roman ship \u003cem\u003eJulia Felix\u003c/em\u003e: glass-water oxygen isotope exchange. Chemical Geology 211, 335\u0026ndash;342, (2004).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMatthews, B. E. \u003cem\u003eet al.\u003c/em\u003e Micro- and Nanoscale Surface Analysis of Late Iron Age Glass from Broborg, a Vitrified Swedish Hillfort. Microscopy and Microanalysis 29, 50\u0026ndash;68, (2023).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKresten, P., Kero, L. \u0026amp; Chyssler, J. Geology of the vitrified hill-fort Broborg in Uppland, Sweden. Geologiska F\u0026ouml;reningen i Stockholm F\u0026ouml;rhandlingar 115, 13\u0026ndash;24, (1993).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eVicenzi, E. P. \u003cem\u003eet al.\u003c/em\u003e Major to Trace Element Imaging and Analysis of Iron Age Glasses Using Stage Scanning in The Analytical Dual Beam Microscope (tandem). Heritage Science 10, 90, (2022).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMarcial, J. \u003cem\u003eet al.\u003c/em\u003e Effect of network connectivity on behavior of synthetic Broborg hillfort glasses. Journal of the American Ceramic Society 106, 1716\u0026ndash;1731, (2023).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eUS DOE. Performance Assessment for the Integrated Disposal Facility, Hanford Site. Report No. RPP-RPT-59958, Rev. 1, (Washington River Protection Solutions, LLC, Richland, WA, 2018).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBagwell, C. E. in \u003cem\u003eMicrobial biotechnology: energy and environment\u003c/em\u003e (ed Rajesh Arora) Going extreme for small solutions to big environmental challenges 363\u0026ndash;381 (Savannah River National Laboratory, 2011).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eWeaver, J. L. \u003cem\u003eet al.\u003c/em\u003e Microbial interactions with silicate glasses. npj Materials Degradation 5, 11, (2021).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eFoster, L. \u003cem\u003eet al.\u003c/em\u003e Microbial bloom formation in a high pH spent nuclear fuel pond. Science of The Total Environment 720, 137515, (2020).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eFredrickson, J. K. \u003cem\u003eet al.\u003c/em\u003e Geomicrobiology of high-level nuclear waste-contaminated vadose sediments at the hanford site, washington state. Applied Environmental Microbiology 70, 4230\u0026ndash;4241, (2004).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eU.S. DOE. Hanford Site Groundwater Monitoring Report for 2017. Report No. DOE/RL-2017-66, Rev. 0, (US Department of Energy, Richland Operations Office, Richland, Washington, USA, 2018).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKim, J.-S., Kwon, S.-K., Sanchez, M. \u0026amp; Cho, G.-C. Geological storage of high level nuclear waste. KSCE Journal of Civil Engineering 15, 721\u0026ndash;737, (2011).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePierce, E. M. \u003cem\u003eet al.\u003c/em\u003e Waste Form Release Data Package for the 2005 Integrated Disposal Facility Performance Assessment. Report No. PNNL-14805, (Pacific Northwest National Laboratory, Richland, WA, USA, 2004).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eThorpe, C. L. \u003cem\u003eet al.\u003c/em\u003e Microbial interactions with phosphorus containing glasses representative of vitrified radioactive waste. Journal of Hazardous Materials 462, 132667, (2024).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eGrahame, M. \u003cem\u003eCharting the UK's changing climate, UK Meteorlogical Office News\u003c/em\u003e, \u0026lt;\u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://www.metoffice.gov.uk/about-us/press-office/news/weather-and-climate/2021/9120-new-climate-normal\u0026gt;\u003c/span\u003e\u003cspan address=\"https://www.metoffice.gov.uk/about-us/press-office/news/weather-and-climate/2021/9120-new-climate-normal%3E\" targettype=\"URL\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e (2021).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eColman, S. M., Platt Bradbury, J. \u0026amp; Rosenbaum, J. G. Paleolimnology and paleoclimate studies in Upper Klamath Lake, Oregon. Journal of Paleolimnology 31, 129\u0026ndash;138, (2004).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eSteinman, B. A. \u003cem\u003eet al.\u003c/em\u003e 1,500 year quantitative reconstruction of winter precipitation in the Pacific Northwest. \u003cem\u003eProceedings of the National Academy of Sciences\u003c/em\u003e 109, 11619\u0026ndash;11623, (2012).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eB\u0026uuml;ntgen, U. \u003cem\u003eet al.\u003c/em\u003e 2500 Years of European Climate Variability and Human Susceptibility. Science 331, 578\u0026ndash;582, (2011).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003e\u0026Aring;berg, G. Precambrian geochronology of south-eastern Sweden. Geologiska F\u0026ouml;reningen i Stockholm F\u0026ouml;rhandlingar 100, 125\u0026ndash;154, (1978).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eLundegardh, P. H. Petrology of the Uppsala Region Eastern Sweden. Swedish Geological Survey 544, 1\u0026ndash;17, (1956).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKatrantsiotis, C. \u003cem\u003ePaleoenvironment and shore displacement since 3200 BC in the central part of the L\u0026aring;nghundraleden Trail, SE Uppland\u003c/em\u003e Masters thesis, Stockholm University, (2013).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBeyth, M., Segev, A. \u0026amp; Bartov, Y. Geological Map of Israel 1:50,000 Be'er Ora Sheet 25-IV. Geological Survey of Israel Maps, (1999).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMart, Y. \u0026amp; Horowitz, A. The tectonics of the Timna region in southern Israel and the evolution of the Dead Sea rift. Tectonophysics 79, 165\u0026ndash;199, (1981).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eGarfunkel, Z. \u0026amp; Ben-Avraham, Z. The structure of the Dead Sea basin. Tectonophysics 266, 155\u0026ndash;176, (1996).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMacLeod, N. S., Sherrod, D. R., Chitwood, L. A., \u0026amp; Jensen, R. A.. Geologic map of Newberry volcano, Deschutes, Klamath, and Lake Counties, Oregon. Report No. I-2455 (Sheet 1 \u0026amp; 2). (1995).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHildreth, W. Quaternary magmatism in the Cascades\u0026mdash;Geologic perspectives. US Geological Survey Professional Paper 1744, (2007).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003ePriest, G. R. Volcanic and tectonic evolution of the Cascade volcanic arc, central Oregon. Journal of Geophysical Research: Solid Earth 95, 19583\u0026ndash;19599, (1990).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eBowles-Martinez, E. \u0026amp; Schultz, A. Composition of Magma and Characteristics of the Hydrothermal System of Newberry Volcano, Oregon, From Magnetotellurics. Geochemistry, Geophysics, Geosystems 21, e2019GC008831, (2020).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eKondracki, J. Regional geography of Poland. \u003cem\u003ePWN, Warsaw (in Polish)\u003c/em\u003e, (2002).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eStevenson, I. \u0026amp; Gaunt, G. D. Geology of the country around Chapel en le Frith. Explanation of one-inch geological sheet 99, New Series. (1971).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eHose, T. A. The English Peak District (as a potential geopark): Mining geoheritage and historical geotourism. Acta Geoturistica 8, 32\u0026ndash;49, (2017).\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eDunham, K. A recent deep borehole near Eyam, Derbyshire. Nature Physical Science 241, 84\u0026ndash;85, (1973).\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"npj-materials-degradation","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"npjmatdeg","sideBox":"Learn more about [npj Materials Degradation](http://www.nature.com/npjmatdeg/)","snPcode":"41529","submissionUrl":"https://submission.springernature.com/new-submission/41529/3","title":"npj Materials Degradation","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"NPJ","inReviewEnabled":true,"inReviewRevisionsEnabled":true},"keywords":"archeological glasses, natural glasses, alteration layers, radioactive waste disposal","lastPublishedDoi":"10.21203/rs.3.rs-5744111/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-5744111/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eHundreds of thousands of cubic meters of legacy radioactive waste from plutonium production stored at U.S. Department of Energy\u0026rsquo;s Hanford site will be immobilized in glass for disposal. The glass must limit radionuclide release into the environment for thousands of years, which is challenging to assess in laboratory experiments. Long-term alteration behavior of analogue glasses can demonstrate how radioactive waste glass will perform over extended periods. Glasses buried for hundreds of years at climatically variable sites were selected for analysis, based on their fulfillment of criteria to be analogues for waste glass. Glass surficial layers were characterized using tomography, SEM, and XRD. The thickness, chemistry and morphology of alteration layers are discussed in terms of sample chemistry and burial conditions. A key finding is that glass in arid environments, e.g., Timna (Israel), exhibits thinner surface layers (~\u0026thinsp;2 \u0026micro;m) compared to glass altered in humid conditions, e.g., Dobkowice (Poland) (up to 59 \u0026micro;m), confirming the significant role of environmental factors in glass durability. However, the correlation between sample age and alteration layer thickness was less strong, challenging the assumption that older samples would have more extensive alteration. Newberry (USA) obsidian (1,350 years old) had alteration layers\u0026thinsp;~\u0026thinsp;15 \u0026micro;m, while Broborg (Sweden) glass (1,500 years old) exhibited layers as thin as 8 \u0026micro;m. Quantification of archeological and natural analogue glass alteration upon exposure to variable environmental factors provides a unique insight into long-term glass alteration. These findings support use of glass for radioactive waste disposal at Hanford and are applicable globally to disposal in near surface facilities.\u003c/p\u003e","manuscriptTitle":"Alteration of archeological and natural analogues for radioactive waste glass under different environmental conditions","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-01-08 11:52:13","doi":"10.21203/rs.3.rs-5744111/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-01-30T11:11:48+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-01-29T20:31:05+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-01-28T16:50:10+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"322822464124124259321654728542051151954","date":"2025-01-09T11:43:33+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"43563264019360969401815145413023653761","date":"2025-01-08T09:10:03+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-01-07T15:03:09+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-01-06T22:48:05+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-01-06T12:10:57+00:00","index":"","fulltext":""},{"type":"submitted","content":"npj Materials Degradation","date":"2025-01-01T01:09:38+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"npj-materials-degradation","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"npjmatdeg","sideBox":"Learn more about [npj Materials Degradation](http://www.nature.com/npjmatdeg/)","snPcode":"41529","submissionUrl":"https://submission.springernature.com/new-submission/41529/3","title":"npj Materials Degradation","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"NPJ","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"c33b9ab4-8783-4573-ae25-9199e52a99b1","owner":[],"postedDate":"January 8th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[{"id":42507061,"name":"Earth and environmental sciences/Environmental sciences/Environmental chemistry/Pollution remediation"},{"id":42507062,"name":"Physical sciences/Energy science and technology/Nuclear energy/Nuclear waste"}],"tags":[],"updatedAt":"2025-08-11T16:04:22+00:00","versionOfRecord":{"articleIdentity":"rs-5744111","link":"https://doi.org/10.1038/s41529-025-00624-4","journal":{"identity":"npj-materials-degradation","isVorOnly":false,"title":"npj Materials Degradation"},"publishedOn":"2025-08-05 15:58:08","publishedOnDateReadable":"August 5th, 2025"},"versionCreatedAt":"2025-01-08 11:52:13","video":"","vorDoi":"10.1038/s41529-025-00624-4","vorDoiUrl":"https://doi.org/10.1038/s41529-025-00624-4","workflowStages":[]},"version":"v1","identity":"rs-5744111","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-5744111","identity":"rs-5744111","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}