Glass Alteration Research Articles

Formation of authigenic titania during the alteration of volcanic glasses in modern deep-sea environments

Titanium (Ti), a typical rock-forming element, is traditionally considered to be lithophile, incompatible, and fluid-immobile, and is recognized as a significant proxy for understanding the oceanic environments, such as the content of terrestrial materials in modern marine sediments. However, recent investigations have revealed the production of various titania minerals through the alteration of volcanic rocks. Considering the occurrence of abundant volcanic rocks (e.g., volcanoclastics, seamounts, and oceanic crusts) in the oceanic environments, the activities of Ti may have been underestimated. Our study provides novel findings on the occurrence and growth mechanism of authigenic titania in the completely altered volcanic glasses collected from Line and Marshall seamounts by using multiple microanalytical methods. Both specimens primarily consist of mixed-layer illite/smectite (I/S), phillipsite, and carbonate-bearing fluorapatite, revealing that the volcanic glasses underwent palagonization processes. Scanning electron micrographs reveal numerous spherical Ti-rich shells with thicknesses of 450–1000 nm, enveloping spherical mixed-layer I/S aggregates with diameters of dozens to hundreds of microns. From the center to the edge of the spherule-shell structures, the concentration of Ti significantly increased. Further analysis using transmission electron microscopy confirms the presence of authigenic Fe-bearing titania particles within these Ti-rich shells. These titania shells likely form as a result of the migration of dissolved Ti(IV) ions and titania nanoparticles, which fill, nucleate, and aggregate at the interfaces of microspherules originally present in the volcanic glasses, ultimately coalescing into micron-sized particles through oriented attachment. Additionally, numerous titania nanoparticles, with aggregate sizes of 4–32 nm, were observed in the pore spaces of the mixed-layer I/S aggregates, likely be those trapped during Ti migration. Brookite is the dominant titania phase in both the titania shells and the smectite pores, with rutile and anatase occasionally present in the titania shells, implying the continuous mineral phase evolution during the growth of titania particles. The occurrence and distribution of titania suggest short-distance migration of Ti during palagonization processes. These findings offer new insight into the brookite formation and the Ti mobilization in basic and oxygen-rich marine environments, which is crucial for understanding the marine geochemical behaviors of Ti.

Nuclear waste glass alteration under the influence of iron, claystone, and cementitious grout: An integral study

To prepare for the future deep geological disposal of high-level waste, the alteration of two inactive nuclear glasses was studied in the presence of claystone, iron, and cementitious grout at 50 °C for a period of 4 years. The materials were immersed together in a synthetic water representative of claystone solution composition. Blank experiments were also carried out to study the independent behaviors of iron and glass in the synthetic water. The evolution of the solutions’ chemistry was monitored. At the end of the experiments, the glass and iron, as well as the neoformed phases, were characterized. Results showed that Si, Ca, Mg, and Fe are key elements. A competition exists between the retention/integration of species into glass gels and clay-like neoformations. Magnesium tends to be leached from glasses and form Mg-silicates. It would only integrate into the gel if it was widely available in the solution. Furthermore, iron could form Fe-silicates. Whether for Mg or Fe, the formation of silicates was detrimental to the glass since it involved the creation of a silicon sink and thus the conservation of a high alteration rate. Concerning calcium, in these experiments it appeared that this species tends to be integrated/retained within the gels. In the pH conditions existing here, it seems that there is no competition with a neoformation. The specific impact of the cementitious grout was also studied, and the results showed that the presence of this material in the system had a beneficial effect on glass alteration due to a significant Si supply in the solution, enabling a reduction in the glass alteration rate.

Effect of structural disorder induced by external irradiation with heavy ions on the alteration of a four oxide borosilicate glass

The irradiation of glass by heavy ions induces structural damage, generally leading to a decrease in its chemical durability whose amplitude strongly depends on the glass chemical composition. Here, we investigate the effects of irradiation by 7 MeV Au ions (simulating the main ballistic effects induced by self-irradiation in nuclear glass) on the behavior of a 4-oxide borosilicate glass in both the initial and residual dissolution regimes. The comparison between irradiated and non-irradiated glasses provides insights into the predominant atomic mechanisms governing glass alteration processes. The most pronounced effect is observed on interdiffusion in acidic conditions, with the rate increased by more than an order of magnitude for the irradiated glass. We show that both the interdiffusion regime and the residual regime are controlled by the hydrolysis of the B—O—Si linkages, whereas under initial dissolution rate regime in basic conditions the rate-limiting step becomes the hydrolysis of Si—O—Si linkages. Overall, the observations suggest structural disorder due to external irradiation by Au ions primarily affects the kinetics of glass alteration without changing the fundamental nature of the limiting reactions.

Soils on Recent Tephra of the Somma–Vesuvius Volcanic Complex, Italy

The Somma–Vesuvius volcanic complex emitted huge quantities of volcanic materials over a period from before 18,300 years BP to 1944. The activity during the last period, from post-AD 1631 to 1944, primarily produced lava and pyroclastics via effusive and strombolian eruptions. We investigated the pedogenesis on rocks formed from post-AD 1631 to 1944, occurring on the slopes of Mt. Vesuvius up to Gran Cono Vesuviano and in the northern valley separating Vesuvius from the older Mt. Somma edifice. Pertinent morphological, physical, chemical, and mineralogical (XRD and FT-IR) soil properties were studied. The results indicated the existence of thin and deep stratified soils on lava, as well as the presence of loose detritic covers formed via pyroclastic emplacement and redistribution. The soils showed minimal profile differentiation, frequently with layering recording the episodic addition of sediments. We found that the dominant coarse size of primary mineral particles was preserved, and there was a low level of clay production. The main mineralogical assemblage present in sands also persisted in clays, indicating the physical breaking of the parent material. Chemical weathering produced mineral modifications towards the active forms of Al and Fe and was also attested in selected soils by glass alteration, allophane production, and the presence of analcime in clay as a secondary product from leucite. The differences in glass alteration and analcime production found in the selected soils on lava were related to soil particle size and soil thickness. Concerning the youngest soil present on Gran Cono Vesuviano, other factors, such as the substratum’s age and site elevation, appeared to be implicated.

Unveiling the effect of composition on nuclear waste immobilization glasses’ durability by nonparametric machine learning

Ensuring the long-term chemical durability of glasses is critical for nuclear waste immobilization operations. Durable glasses usually undergo qualification for disposal based on their response to standardized tests such as the product consistency test or the vapor hydration test (VHT). The VHT uses elevated temperature and water vapor to accelerate glass alteration and the formation of secondary phases. Understanding the relationship between glass composition and VHT response is of fundamental and practical interest. However, this relationship is complex, non-linear, and sometimes fairly variable, posing challenges in identifying the distinct effect of individual oxides on VHT response. Here, we leverage a dataset comprising 654 Hanford low-activity waste (LAW) glasses across a wide compositional envelope and employ various machine learning techniques to explore this relationship. We find that Gaussian process regression (GPR), a nonparametric regression method, yields the highest predictive accuracy. By utilizing the trained model, we discern the influence of each oxide on the glasses’ VHT response. Moreover, we discuss the trade-off between underfitting and overfitting for extrapolating the material performance in the context of sparse and heterogeneous datasets.

Material and mechanical properties of young basalt in drill cores from the oceanic island of Surtsey, Iceland

Characterization of 2017 drill core samples from Surtsey, an oceanic island produced by 1963−1967 eruptions in the offshore extension of Iceland’s east rift zone, reveals highly heterogeneous microstructural, physical, and mechanical properties in subaerial, submarine, and subseafloor basaltic deposits. The connected porosity varies from 42% in weakly consolidated lapilli tuff in a submarine inflow zone to 21% in strongly lithified lapilli tuff in upper subseafloor deposits near the explosively excavated conduit. Permeability, however, varies over six orders of magnitude, from 10−18 m2 to 10−13 m2. Uniaxial compressive strength, P-wave velocity, and thermal conductivity are also highly variable: 10−70 MPa, 1.48−3.74 km·s−1, and 0.472−0.862 W·m−1·K−1, respectively. Synchrotron X-ray microdiffraction analyses integrated with major-element geochemistry and quantitative X-ray powder diffraction analyses describe the initial alteration of fresh glass, incipient consolidation of a fine-ash matrix, and partial closure of pores with mineral cements. Permeability, micromechanical, and thermal property modeling highlight how porosity and pore size in eruptive fabrics—modified through diverse cementing microstructures—influence the physical properties of the pyroclastic deposits. Borehole temperatures, 25−141 °C (measured from 1980 to 2018), do not directly correlate with rock strength properties; rather, the abundance and consolidation of a binding fine-ash matrix appears to be a primary factor. Analytical results integrated with archival data from 1979 drill core samples provide reference parameters for geophysical and heat transfer studies, the physical characteristics of pyroclastic deposits that lithify on a decadal scale, and the stability and survival of oceanic islands over time.

The use of glasses from archeological sites to understand the long-term alteration of nuclear waste glasses

The use of glasses from archeological sites to understand the long-term alteration of nuclear waste glasses

Authigenic mineralization in Surtsey basaltic tuff deposits at 50 years after eruption

Alteration of basaltic glass and in situ mineral growth are fundamental processes that influence the chemical and material properties of Earth’s oceanic crust. These processes have evolved at the basaltic island of Surtsey (SW Iceland) since eruptions terminated in 1967. Here, subaerial and submarine lapilli tuff samples from a 192 m-deep borehole drilled in 2017 (SE-02b) are characterized through petrographic studies, X-ray powder diffraction analyses, and SEM–EDS imaging and chemical analyses. The integrated results reveal (i) multi-stage palagonitization processes in basaltic glass and precipitation of secondary minerals from matrix pore fluids, (ii) multi-stage crystallization of secondary phillipsite, analcime and Al-tobermorite in the vesicles of basaltic pyroclasts and (iii) variations in palagonitization processes as a function of thermal and hydrological domains. Although temperature appears to be an important factor in controlling rates of secondary mineralization, the chemistry of original basaltic components and interstitial fluids also influences reaction pathways in the young pyroclastic deposits. The integration of systematic mineralogical analyses of the 50-year-old tuff from one of the most carefully monitored volcanic sites on Earth, together with temperature monitoring in boreholes since 1980, provide a reference framework for evaluating mineralogical evolution in other Surtseyan-type volcanoes worldwide.

Hyperspectral (VNIR-SWIR) analysis of roll front uranium host rocks and industrial minerals from Karnes and Live Oak Counties, Texas Coastal Plain

VNIR-SWIR (400–2500 nm) reflectance measurements were made on the surfaces of various cores, cuttings and sample splits of sedimentary rocks from the Tertiary Jackson Group, and Catahoula, Oakville and Goliad Formations. These rocks vary in composition and texture from mudstone and claystone to sandstone and are known host rocks for roll front uranium occurrences in Karnes and Live Oak Counties, Texas. Spectral reflectance profiles, 569 in total, were reduced to 125 representative spectral signatures, which were analyzed using the U.S. Geological Survey's (USGS) Material Identification and Characterization Algorithm (MICA). MICA uses an automated continuum-removal procedure together with a least-squares linear regression to determine the fit of observed sample spectral absorption features to those of reference mineral standards in a spectral library. The reference minerals include various clay, mica, carbonate, ferric and ferrous iron minerals and their mixtures. In addition, absorption feature band-depth analysis was done to identify rock surfaces exhibiting absorption features related to uranium and zeolite minerals, which were not included in the command files used to execute MICA.Rocks from each of the four geologic units produced broadly similar spectral signatures as a result of comparable mineral compositions, but there were some notable differences. For example, Ca- and Na-montmorillonite was matched most frequently to the spectral absorption features in 2-μm (∼2000–2500 nm) wavelengths, while goethite occurred often at 1-μm (∼400–1000 nm) wavelengths. The latter is related to limonitic iron-staining in and around oxidized zones of the uranium roll front as described in previous papers. Rocks of the Jackson Group differed from those of the Catahoula, Oakville and Goliad units in that the former exhibited spectral features we interpret as being due to the presence of lignite-bearing mudstone layers. Goliad rocks exhibit spectral features related to dolomite, gypsum, anhydrite, and an unidentified green clay mineral that is possibly glauconite. Jackson Group rocks also exhibit weak but well-resolved absorption features at 964 and 1157 nm related to either or both zeolite minerals clinoptilolite and heulandite. These zeolite minerals and a few spectra exhibiting hydrous silica absorption features are indicative of alteration of volcanic glass in tuffaceous mudstone and claystone layers. A few sample spectra exhibited strong absorption features at around 1135 nm related to the uranium mineral coffinite. Both the 1135 nm coffinite and 1157 nm zeolite absorption features overlap somewhat, potentially making them difficult to distinguish without additional hyperspectral field, laboratory or remote sensing data.The results of this study were compared to mixtures of minerals described for ore, gangue and alteration minerals in deposit models for sandstone-hosted uranium, sedimentary bentonite and sedimentary zeolite. Use of these spectra can help facilitate mapping of both waste materials from the legacy mining of the above commodities, as well as future exploration and resource assessment activities.

Reaction mechanisms in hydrated magnesium silicate glass investigated by Ab-Initio methods and Metadynamics

In the field of magnesium-containing silicate glass alteration under aqueous conditions, enstatite glass (MgSiO3) is used as a valuable system to investigate reaction pathways occurring in its hydrated form by means of Ab-Initio methods. In contrast to previous dissolution studies in which the water molecules interacted only at the glass surface or with small molecular clusters, here we follow reaction pathways for water molecules introduced in the voids of a realistic glass structure. Metadynamics combined with atomic charges derived from electrostatic potential suggest that water dissociation follows a two-step scheme: at first, the water molecule interacts with a SiO4 or MgOx(x≥3) structural unit via dipole–dipole or dipole–charge interactions, and second, a proton transfer occurs. It also appears that SiOH-Mg hydrolysis reactions are the more likely to occur. Furthermore, it is inferred that pathways exist for complete H2O dissociation in two H+ and one O2− ions, leading to new bonding between the free oxygen ion and Si or Mg cations forming the network. This phenomenon could probably counterbalance hydrolysis and depolymerization by increasing again network connectivity. Several bond dissociation energies are evaluated and the MgO bond dissociation enthalpy from the MgOHSi linkage is derived to be 1.34 eV (or 128.84 kJ mol−1).

Impact of gold ion irradiation on the initial alteration rate of the International Simple Glass

This study addresses the impact of 7 MeV Au irradiation on the initial alteration rate of International Simple Glass (ISG), considered as a reference for nuclear glasses. This irradiation scenario simulates the effect of nuclear collisions of the recoil nuclei of α decays. In order to study the very first moments of glass alteration, non-irradiated and Au-ion irradiated ISG glass monoliths were altered in pure water at 90 °C, pH 9 and with a ratio of glass surface area to solution volume of 0.01 cm−1. Glass alteration was monitored by measuring the releases of the glass elements in solution by UV–visible spectrophotometry and Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES). Under these alteration conditions, the releases of the elements in solution are congruent. The initial alteration rate was found to be (2.0 ± 0.8) times higher for the irradiated glass monoliths than for non-irradiated samples.

Characterization and Origin of Basalt-Derived Carnelian in the Mesozoic Newark Basin, New Jersey, USA

Carnelian occurs locally in New Jersey in the Newark basin as medium- to coarse-size pebbles in fluvial gravel and alluvium and colluvium formed from erosion of Lower Jurassic Preakness Basalt. Vesicles and molds of glauberite are preserved on lower surfaces and botryoidal textures on the upper surfaces of some pieces. The microstructure consists of length-fast chalcedony characterized by parallel fibrous bundles overlain by repetitive, wavy extinction bands. Only peaks of ɑ-quartz and minor moganite are recognized in X-ray diffraction patterns. Carnelian contains 97–98 wt.% SiO2, ~1.0 wt.% Fe2O3, and 1.0–1.4 wt.% LOI; other major elements are <0.1 wt.%. Trace element abundances are low except for Y, Nb, Ta, W, Th, and U. Rare earth element (REE) patterns display heavy REE enrichment and large negative Eu anomalies. Most trace elements were mobilized from Proterozoic sources, whereas Si was likely derived from the alteration of basaltic glass in the Preakness. Carnelian δ18OVSMOW values are high and range from +18.3 to +31.2‰, comparable to global occurrences of volcanic rock-derived chalcedony. We propose that carnelian precipitated in the first Preakness flow from the mixing of hydrothermal fluid with meteoric water under conditions of low temperature (20–80 °C) and neutral to slightly alkaline pH.

Influence of humidity in the alteration of unstable glasses

AbstractThe control of humidity between certain limits is essential to avoid the alteration of historical objects, such as unstable historical glasses. However, the usual limits can be altered due to the presence of volatile organic compounds. This work presents the results of the exposure of soda, potash, and mixed‐alkali silicate glasses to neutral and acidic (formic) atmospheres with ∼30%, ∼70%, and ∼100% relative humidity. The hygroscopic capacity of the glass was analyzed by gravimetry, and the surface alteration was evaluated by infrared spectroscopy, optical microscopy, and ion chromatography. In all glasses, the alteration begins with alkali ions’ lixiviation followed by the silica network's hydrolytic attack. The results showed that soda and mixed‐alkali silicate glasses exhibit similar behavior, while the potash‐lime one experienced the fastest degradation due to its composition. Results also confirmed that high humidity increased the alteration rate causing a higher hygroscopicity and reactivity of glasses. Finally, acidic environments promoted the ion‐exchange reaction at high humidity, accelerating the lixiviation of alkaline ions and promoting the diffusion of water into the glass network.

The parent bodies of CR chondrites and their secondary history

AbstractRenazzo‐type (CR) chondrites are a relatively rare group of carbonaceous chondrites with the vast majority having escaped thermal alteration. This means that CRs are composed of relatively unprocessed material, depending on the extent of aqueous alteration they have experienced. Hydration in CRs ranges from incipient alteration of matrix glass, up to nearly complete replacement of the rock by hydration products. The extent of secondary processes is often difficult to assess in these meteorites, due to their heterogeneity and diversity of alteration products. Yet, this is crucial in order to understand the extent of geological processing that occurred on the primary parent body. Additionally, the parent asteroids of CRs remain a mystery, mainly because terrestrial oxyhydroxide signatures dominate the reflectance spectra of CRs. In this work, we have conducted optical and IR reflectance and transmission spectra of 25 CR chondrites in order to (i) better evaluate the extent of aqueous alteration that occurred on the CR parent body, and (ii) find possible parent body candidates. Terrestrial oxyhydroxides were removed from 12 samples, as these tend to interfere with the optical‐IR spectra of CRs. Our results suggest, among other, that (i) aqueous alteration in most of our CRs was limited to the matrix and (ii) most CRs may stem from a continuum of X‐to‐C complex asteroids, depending on their extent of aqueous alteration. More specifically, the endmembers being Xk/Xn types and Cgh/Ch types. This has strong implication in regard to what we can expect from the Psyche mission.

Compositional changes by SIMS and XPS analyses on fresh and aged Roman-like glass

This study reports important analytical evidence of an unusual non-uniform element distribution in the superficial layers of glass matrices (from few nm up to 1 µm). The unforeseen observation was made on silica-soda-lime glass mock-ups before and after their artificial ageing, using secondary ion mass spectrometry (SIMS) and X-ray photoelectron spectroscopy (XPS) surface analysis techniques. The analyses showed a marked non-homogeneous element distribution at the glass surface. The results indicated a very low concentration of Na at the surface up to a depth of around 500 nm below the surface, where its concentration increases reaching a plateau. In addition, the profile distribution of H in the first 200 nm of the pristine glass surface indicated a diffusion of hydrogen from the surrounding environment to the glass network. Additional modifications during the glass ageing process related to external factors (such as temperature and humidity) were also identified in relation to sodium atoms, with atoms on the glass surface showing a different chemical state from those in the bulk. This study confirms that glass composition as well as glass alteration are non-homogeneous locally supporting the importance of studying glass surface as region of interaction with surrounding environment.

Long-Term Chemical Alteration of 238Pu-Doped Borosilicate Glass in a Simulated Geological Environment with Bentonite Buffer

Chemical degradation of borosilicate glass doped with 238Pu was modelled in conditions of a failed underground radwaste repository in granite host rock with bentonite buffer material after penetration of aqueous solutions at temperature of 90 °C. The total duration of the experiment exceeded two years. It is shown that wet bentonite preserved its barrier function and prevents migration of plutonium to the solution. The total amount of plutonium adsorbed on bentonite clay during the experiment did not exceed 0.02% of the initial amount of plutonium in the glass sample. Estimated accumulated dose of self-irradiation of the glass sample after the experiment varies from 3.16 × 1015 to 3.39 × 1015 α-decays per gram, which is equivalent to more than 1000 years storage of 239Pu doped sample with the same Pu content. Beishan granite remained intact, with no evidence of Pu penetration into the granite matrix along mineral grain boundaries.

Improved collection of rooftop micrometeorites through optimized extraction methods: The Budel collection

AbstractThe scientific value of micrometeorites collected from deep‐sea sediments or glacial deposits can be limited by poorly constrained accumulation times or severe alteration, coupled with a complex infrastructure of sampling expeditions. Collecting micrometeorites from rooftops has recently become a feasible alternative, but extraction methods have not been optimized or standardized to date. Here, we show that existing methods for the recovery of melted cosmic spherules (CSs) can be strongly improved by using a sequence of mineral separation techniques, including shape separation with an asymmetric vibrator and heavy liquid density separation with overflow centrifuges. We retrieved 1006 micrometeorites from the gutter of a barn in Budel, the Netherlands. Particle diameters are 80–515 μm, with the major mode at 130 μm and a slope exponent of −4.88. Differences in size distributions among various types of CSs indicate a multi‐source influx, with CS textures controlled by their parent body's mineralogy and orbital parameters. Repeated sampling of the rooftop after accumulation times of 959 and 333 days allows for a time‐integrated global mass flux estimate of 472 t year−1. This estimate is notably higher than previous rooftop‐based estimates but is still severely affected by micrometeorite loss from the gutter through drainage. The mass flux peaks at an equivalent particle diameter of ~200 μm. The Budel collection is the first rooftop collection to contain abundant vitreous micrometeorites and include the coarse‐grained S‐type CS class. Unmelted and I‐type micrometeorites remain difficult to extract from rooftop samples. Vitreous micrometeorites display various stages of weathering, showing that severe alteration of glass can progress at a faster rate in populated regions than previously assumed. This study demonstrates that methodological adjustments can drastically increase the scientific potential of rooftop micrometeorite collections.

Phyllosilicate formation on early Mars via open-system acid alteration of basaltic glass

Smectites are widespread on Mars, but the water-rich, neutral-to-alkaline pH conditions favorable for smectite formation would be expected to have also produced abundant carbonates on early Mars, which are not observed. Smectite formation from basaltic glass on Mars could occur in acidic environments unfavorable for carbonate formation. Acidic smectite formation has been previously demonstrated in batch experiments (closed hydrologic systems), however, the mechanisms and octahedral composition of smectite forming in acidic flow-through (open hydrologic systems) environments are still not fully understood. We conducted hydrothermal (190°C) alteration experiments on Stapafell basaltic glass at 0.01 and 0.25 mLmin−1 flow rates corresponding to low and high water to rock ratio (W/R) flow conditions, and initial pH (pH0) values of 2, 3, 4 and 6. A batch low W/R experiment was conducted at pH0 2 for comparison to the open system experiment. Kaolinite, montmorillonite and chlorite formed at pH0 2 at low W/R; no phyllosilicates formed at pH0 2 at high W/R; and lizardite formed at pH0 ≥ 3 at both W/R ratios. Lizardite, kaolinite, and montmorillonite in these experiments formed by precipitation from solution and chlorite likely formed through alteration of montmorillonite and/or basalt. Saponite formed at pH0 2 in batch conditions by alteration of basaltic glass. Comparison of experimental data with martian observations of phyllosilicate assemblages indicated that smectite formation on Mars likely occurred under water-limited environmental conditions. Al-rich smectite could form in low W/R open system subsurface environments under a very narrow range of pH (pH < 3) while saponite could form in closed low W/R systems under acidic to alkaline conditions. The combination of open and closed hydrological regimes could be responsible for development of clay mineral stratigraphies observed on Mars. The acidic conditions required for formation of Al-rich smectite montmorillonite were unfavorable for carbonate precipitation, but carbonate precipitation could occur together with Fe/Mg-smectite saponite in closed systems at pH > 4. The lack of widespread carbonates on Mars could not therefore be explained solely by acidic conditions. Phyllosilicate formation under acidic conditions on Mars may affect biosignature stability in martian regolith as preservation capacity is lower in phyllosilicates that formed in or experienced acidic pH.

Micro- and Nanoscale Surface Analysis of Late Iron Age Glass from Broborg, a Vitrified Swedish Hillfort

AbstractArchaeological glasses with prolonged exposure to biogeochemical processes in the environment can be used to understand glass alteration, which is important for the safe disposal of vitrified nuclear waste. Samples of mafic and felsic glasses with different chemistries, formed from melting amphibolitic and granitoid rocks, were obtained from Broborg, a Swedish Iron Age hillfort. Glasses were excavated from the top of the hillfort wall and from the wall interior. A detailed microscopic, spectroscopic, and diffraction study of surficial textures and chemistries were conducted on these glasses. Felsic glass chemistry was uniform, with a smooth surface showing limited chemical alteration (&amp;lt;150 nm), irrespective of the position in the wall. Mafic glass was heterogeneous, with pyroxene, spinel, feldspar, and quartz crystals in the glassy matrix. Mafic glass surfaces in contact with topsoil were rougher than those within the wall and had carbon-rich material consistent with microbial colonization. Limited evidence for chemical or physical alteration of mafic glass was found; the thin melt film that coated all exposed surfaces remained intact, despite exposure to hydraulically unsaturated conditions, topsoil, and associated microbiome for over 1,500 years. This supports the assumption that aluminosilicate nuclear waste glasses will have a high chemical durability in near-surface disposal facilities.

Radiogenic Nd in bioapatite from rare earth elements rich deep sea sediments from Central Indian Oceanic Basin and its implication in material sources

Rare Earth Element and Yttrium (REY)-rich deep sea sediments have been estimated to be a highly important potential resource. However, the main material sources that supply the huge amount of REY resources, as well as geochemical procedure determines the distinct REY patterns of these sediments, remain unclear. To fill this research gap, in this study, three sediment cores (GC02, GC04, and GC11) collected from the Central Indian Ocean Basin (CIOB) and a core (GC03) from eastern of the 90° E Ridge (NER) were sampled for mineral identification and elemental (major, trace, and rare earth elements) analyses. Fish teeth and detrital minerals were isolated from the sediments, and their 87Sr/86Sr and 143Nd/144Nd ratios were measured. Accumulation of REY is revealed in three cores of GC02, GC04, and GC11 from CIOB with mean value of 511.93 μg/g, 614.79 μg/g, and 1036.14 μg/g, respectively. Most REY rich sediment exhibit obvious to slight negative Ce abnormal, slight positive Eu and Y abnormal. The detrital fraction of the REY rich sediments exhibit less radioactive εNd values of − 8.36295 and more radioactive 87Sr/86Sr of of 0.71651. On the contrary, the fish teeth exhibit less radiogenic 87Sr/86Sr ratio of 0.70915 but more radiogenic εNd values of − 5.13511 than those of the sea water of the Indian Ocean. The results reveal that the REY-rich sediments in the CIOB are characterized by multiple material sources including weathering continental products, alteration of volcanogenic glasses, hydrothermal and marine authigenic materials. Distinct volcanogenic materials input are obvious in the CIOB evidenced with radiogenic 143Nd/144Nd ratios of the fish teeth, the wide occurrence of clinoptilolite and high Te contents contained. The volcanogenic related hydrothermal materials are then indicated to provide most part of REY for the fish teeth, which contribute the most amount of REY of the sediments. However, the terrestrial input of REY cannot be neglected, which indicates the REY-rich deep sediments were formed under multi-source supply system. The study indicated that continuous exchange of Sr between fish teeth and ambient pore water after deposition, and ambient pore water was concluded to contain an abundance of released radiogenic terrestrial Sr. However, the exchange of Nd between fish teeth and bottom sea water ceased after buried in depth. Nd ratios on the fish teeth recorded the more radioactive hydrothermal material carried by bottom seawater at the early stage of precipitation.