Dissolution of basalts and peridotite in seawater, in the presence of ligands, and CO2: Implications for mineral sequestration of carbon dioxide

Steady-state silica release rates (r_Si) from basaltic glass and crystalline basalt of similar chemical composition as well as dunitic peridotite have been determined in far-from-equilibrium dissolution experiments at 25 °C and pH 3.6 in (a) artificial seawater solutions under 4 bar pCO₂, (b) varying ionic strength solutions, including acidified natural seawater, (c) acidified natural seawater of varying fluoride concentrations, and (d) acidified natural seawater of varying dissolved organic carbon concentrations. Glassy and crystalline basalts exhibit similar r_Si in solutions of varying ionic strength and cation concentrations. Rates of all solids are found to increase by 0.3-0.5 log units in the presence of a pCO₂ of 4 bar compared to CO₂ pressure of the atmosphere. At atmospheric CO₂ pressure, basaltic glass dissolution rates were most increased by the addition of fluoride to solution whereas crystalline basalt rates were most enhanced by the addition of organic ligands. In contrast, peridotite does not display any significant ligand-promoting effect, either in the presence of fluoride or organic acids. Most significantly, Si release rates from the basalts are found to be not more than 0.6 log units slower than corresponding rates of the peridotite at all conditions considered in this study. This difference becomes negligible in seawater suggesting that for the purposes of in-situ mineral sequestration, CO₂-charged seawater injected into basalt might be nearly as efficient as injection into peridotite.     

Composition-Induced Variations in SIMS Instrumental Mass Fractionation during Boron Isotope Ratio Measurements of Silicate Glasses

An analytical artefact is reported here related to differences in instrumental mass fractionation between NIST SRM glasses and natural geological glasses during SIMS boron isotope determinations. The data presented demonstrated an average 3.4‰ difference between the NIST glasses and natural basaltic to rhyolitic glasses mainly in terms of their sputtering-induced fractionation of boron isotopes. As no matrix effect was found among basaltic to rhyolitic glasses, instrumental mass fractionation of most natural glass samples can be corrected by using appropriate glass reference materials. In order to confirm the existence of the compositionally induced variations in boron SIMS instrumental mass bias, the observed offset in SIMS instrumental mass bias has been independently reproduced in two laboratories and the phenomenon has been found to be stable over a period of more than one year. This study highlights the need for a close match between the chemical composition of the reference material and the samples being investigated.     

Chemical alteration of volcanic glasses and related control by secondary minerals: Experimental studies

A detailed experimental mineralogical and geochemical study on hydrothermal alteration processes of volcanic glasses with a different chemical composition and leucites sampled in the Roman Comagmatic Region was carried out. 2g samples of different grain sizes and 50 ml of deionized water or seawater were sealed in bronze Teflon-lined autoclaves and placed in a rotating sample-holder at 200°C. The internal pressure was 16.2 bars. At arbitrary intervals, the pressure vessel was quenched to room temperature and both solids and solutions were separated by filtration. The solids were used to identify possible alteration products by means of X-ray powder diffraction, SEM and microprobe analyses. In all deionized water systems the contact solution reached pH basic values, but in the various systems the consumption of H⁺ ions occurred in different ways. This is probably linked to different concentrations of released cations. In seawater systems, however, pH values initially fell sharply but subsequently increased slightly. After 2 days, cation concentrations were clearly buffered by reaction products in all solutions. These were mainly zeolites and clay minerals. The following crystallization sequences in all glass/deionized water experiments were observed: the first reaction product was represented by phillipsite, followed by analcime and illite in the alkali-trachytic run; chabasite and analcime in the phonolitic-tephritic run; analcime and finally feldspar in shoshonitic and trachytic runs. Phillipsite and smectite crystallized together only in the basaltic run. In leucite/deionized water systems, however, the first reaction phase was illite, followed by analcime and then phillipsite. The reaction products in glass/seawater systems were smectite and anydrite. The chemical composition of synthetic zeolites was clearly controlled by the chemistry of initial glasses. These synthetic zeolites are like the natural ones in volcaniclastic products from central and southern Italy. This suggests that extensive zeolitization processes of these volcaniclastic rocks may occur through interaction of volcanic glasses with fluids at a very low salinity and a temperature close to 200°C.     

The effect of crystallinity on dissolution rates and CO2 consumption capacity of silicates

Comparison of measured far-from-equilibrium dissolution rates of natural glasses and silicate minerals at 25 °C and pH 4 reveals the systematic effects of crystallinity and elemental composition on these rates. Rates for both minerals and glasses decrease with increasing Si:O ratio, but glass dissolution rates are faster than corresponding mineral rates. The difference between glass and mineral dissolution rates increases with increasing Si:O ratio; ultra-mafic glasses (Si:O ? 0.28) dissolve at similar rates as correspondingly compositioned minerals, but Si-rich glasses such as rhyolite (Si:O ∼ 0.40) dissolve ?1.6 orders of magnitude faster than corresponding minerals. This behaviour is interpreted to stem from the effect of Si-O polymerisation on silicate dissolution rates. The rate controlling step of dissolution for silicate minerals and glasses for which Si:O > 0.28 is the breaking of Si-O bonds. Owing to rapid quenching, natural glasses will exhibit less polymerisation and less ordering of Si-O bonds than minerals, making them less resistant to dissolution. Dissolution rates summarized in this study are used to determine the Ca release rates of natural rocks at far-from-equilibrium conditions, which in turn are used to estimate their CO₂ consumption capacity. Results indicate that Ca release rates for glasses are faster than those of corresponding rocks. This difference is, however, significantly less than the corresponding difference between glass and mineral bulk dissolution rates. This is due to the presence of Ca in relatively reactive minerals. In both cases, Ca release rates increase by ∼two orders of magnitude from high to low Si:O ratios (e.g., from granite to gabbro or from rhyolitic to basaltic glass), illustrating the important role of Si-poor silicates in the long-term global CO₂ cycle.     

The effect of fluoride on the dissolution rates of natural glasses at pH 4 and 25°C

Far-from-equilibrium, steady-state dissolution rates at pH 4 of a suite of natural glasses, ranging from basaltic to rhyolitic in composition, have been determined as a function of aqueous fluoride concentrations up to 1.8 × 10⁻⁴ mol/kg in mixed-flow reactors. Dissolution rates of each of these glasses increase monotonically with increasing aqueous fluoride concentration. Measured dissolution rates are found to be consistent with both the Furrer and Stumm (1986) surface coordination model and the Oelkers (2001) multi-oxide dissolution model. Application of the latter model yields the following equation that can describe all measured rates as a function of both glass and aqueous solution composition:

     

Effects of the peat acid digestion protocol on geochemically and morphologically diverse tephra deposits

Tephra shards for electron probe microanalysis are most efficiently extracted from peat using acid digestion, which removes organic material that hinders density separation methods. However, strong acids are known to alter glass chemical compositions, and several studies have examined how acid digestion affects rhyolitic volcanic glass. The focus on rhyolitic tephra in these studies leaves considerable uncertainty, as the dissolution rates of natural glasses (including tephra) are determined by the chemical composition and surface area/volume ratio, both of which vary in tephra deposits. Here, we use duplicate samples of basaltic, trachydacitic and rhyolitic tephra to examine physical and geochemical alteration following acid digestion. Scanning electron microscope imagery reveals no discernible degradation of glass surfaces, and electron probe microanalysis results from duplicate samples are statistically indistinguishable. These findings suggest the acid digestion protocol for organic peats does not significantly alter glass geochemistry regardless of shard morphologies or geochemical compositions.     

Long-term modeling of alteration-transport coupling: Application to a fractured Roman glass

To improve confidence in glass alteration models, as used in nuclear and natural applications, their long-term predictive capacity has to be validated. For this purpose, we develop a new model that couples geochemical reactions with transport and use a fractured archaeological glass block that has been altered for 1800 years under well-constrained conditions in order to test the capacity of the model.The chemical model considers three steps in the alteration process: (1) formation of a hydrated glass by interdiffusion, whose kinetics are controlled by a pH and temperature dependent diffusion coefficient; (2) the dissolution of the hydrated glass, whose kinetics are based on an affinity law; (3) the precipitation of secondary phases if thermodynamic saturation is reached. All kinetic parameters were determined from experiments. The model was initially tested on alteration experiments in different solutions (pure water, Tris, seawater). It was then coupled with diffusive transport in solution to simulate alteration in cracks within the glass. Results of the simulations run over 1800 years are in good agreement with archaeological glass block observations concerning the nature of alteration products (hydrated glass, smectites, and carbonates) and crack alteration thicknesses. External cracks in direct contact with renewed seawater were altered at the forward dissolution rate and are filled with smectites (400−500 μm). Internal cracks are less altered (by 1 or 2 orders of magnitude) because of the strong coupling between alteration chemistry and transport. The initial crack aperture, the distance to the surface, and sealing by secondary phases account for these low alteration thicknesses. The agreement between simulations and observations thus validates the predictive capacity of this coupled geochemical model and increases more generally the robustness and confidence in glass alteration models to predict long-term behavior of nuclear waste in geological disposal or natural glass in the environment.     

Petrogenesis of a basalt-rhyolite tephra from the west-central Afar,Ethiopia

The Cindery Tuff is an unusual tephra fall deposit that contains evidence for the mixing of basaltic and rhyolitic liquids prior to eruption. It contains clear rhyolitic glass shards together with brown basaltic glass spheres and a broadly bimodal phenocryst assemblage. Brown glasses are ferrobasaltic in composition and are similar to the voluminous Pliocene tholeiites of the surrounding west-central Afar volcanic field; both are enriched in the light rare earth and incompatible elements and possess higher ⁸⁷Sr/⁸⁶Sr and lower ¹⁴³Nd/¹⁴⁴Nd than MORB. Rhyolitic glasses are subalkaline and, compared to the basaltic glasses, are strongly depleted in the compatible elements and enriched in the incompatible elements. Both glass types have similar incompatible element and isotopic ratios, and with the rhyolite glass showing a 2-fold parallel enrichment in rare earth element abundances over the basaltic glass. These observations suggest that the two glasses are genetically related.Rare glasses with intermediate compositions occur as phenocryst melt inclusions, as mantles on phenocrysts and as free pumice clasts. Their major element contents do not point to an origin by simple hybrid mixing of the basaltic and rhyolitic melts. Rather, major element mixing calculations indicate formation of the intermediate and rhyolite melts by fractionation of the observed phenocryst assemblage, using a starting composition of the observed basaltic glass. Model calculations from trace element data, though lacking from the intermediate glasses, support fractional crystallization. The bimodal mineral assemblage argues against an immiscible liquid origin for the contrasting glass compositions.     

A fractured roman glass block altered for 1800 years in seawater: Analogy with nuclear waste glass in a deep geological repository

Fractured archaeological glass blocks altered 1800 years in seawater are investigated because of their morphological analogy with vitrified nuclear waste. They provide an opportunity for understanding glass alteration in variable confined media (cracks), by studying an actual ancient system in a known stable natural environment. Characterization of the crack network from two-dimensional trace maps (length, alteration thickness, orientation) allows us to determine the three-dimensional geometric parameters (crack density, fracture ratio) and the percentage of alteration, using stereological relations. This methodology could be applied to nuclear glass. From a representative archaeological glass block, we showed that the surface developed by the cracks is 86 ± 27 times greater than the geometric surface but the volumetric alteration is 12.2 ± 4.1%, which is only 12 times greater than the volumetric alteration of the block periphery (about 1 vol%). This unexpected low value is explained by the large variation of the alteration thicknesses in the different types of cracks in relation with their location in the block. The alteration thickness is usually smaller in the internal zone than in the border zone. The alteration layers resulted from three main mechanisms (interdiffusion, glass dissolution, and secondary phase precipitation) leading to two different alteration products (a sodium-depleted layer and mainly a Mg-smectite). Geometric parameters such as the glass surface area/solution volume ratio and transport parameters (renewal of the alteration solution) strongly affected the glass dissolution kinetics. The confined conditions and the diffusive transport of reactive species favor low alteration kinetics. The precipitation of secondary phases also results in sealing of the cracks. Consequently, although it is not known if subcritical crack growth occurred, internal cracks account for only a minor contribution to the overall alteration. These results improve our understanding of alteration in cracks for assessing the predominant physical and chemical parameters that must be considered in long-term nuclear glass modeling.     

Influence of composition and thermal history of volcanic glasses on water content as determined by micro-Raman spectrometry

Development of Raman spectrometry for quantification of water content in natural glasses requires the assessment of the dependence of the technique on glass composition and thermal history. In the low frequency domain, Raman spectra topology varies due to glass depolymerization and substitution in the framework of (Si⁴⁺)^IV by alkali-balanced (Al³⁺)^IV and (Fe³⁺)^IV in calcalkaline (rhyolite to basaltic andesite) and alkaline (trachyte, phonolite to alkali basalt) glasses. These processes result in strong dependence of previous analytical procedure (internal calibration) on glass composition. Here, we show that an analytical procedure based on calibration to an external standard is only faintly composition-dependent for Si-rich alkaline glasses (trachytes–phonolites). For a given glass composition, thermal history also plays a fundamental role in the choice of Raman procedure for water analysis. Repeated cycles of thermal annealing induce microcrystallization of hydrous trachyte glasses and modify cation distribution in the glass structure. Application of these concepts to analysis of banded obsidians suggests that small-scale heterogeneities in glasses are not simply related to magma degassing, but could depend on thermal history and consequent relaxation paths in the melt.     

Glasses for immobilization of low- and intermediate-level radioactive waste

Reprocessing of spent nuclear fuel (SNF) for recovery of fissionable elements is a precondition of long-term development of nuclear energetics. Solution of this problem is hindered by the production of a great amount of liquid waste; 99% of its volume is low- and intermediate-level radioactive waste (LILW). The volume of high-level radioactive waste (HLW), which is characterized by high heat release, does not exceed a fraction of a percent. Solubility of glasses at an elevated temperature makes them unfit for immobilization of HLW, the insulation of which is ensured only by mineral-like matrices. At the same time, glasses are a perfect matrix for LILW, which are distinguished by low heat release. The solubility of borosilicate glass at a low temperature is so low that even a glass with relatively low resistance enables them to retain safety of under-ground LILW depositories without additional engineering barriers. The optimal technology of liquid confinement is their concentration and immobilization in borosilicate glasses, which are disposed in shallow-seated geological repositories. The vitrification of 1 m³ liquid LILW with a salt concentration of ～300 kg/m³ leaves behind only 0.2 m³ waste, that is, 4–6 times less than by bitumen impregnation and 10 times less than by cementation. Environmental and economic advantages of LILW vitrification result from (1) low solubility of the vitrified LILW in natural water; (2) significant reduction of LILW volume; (3) possibility to dispose the vitrified waste without additional engineering barriers under shallow conditions and in diverse geological media; (4) the strength of glass makes its transportation and storage possible; and finally (5) reliable longterm safety of repositories. When the composition of the glass matrix for LILW is being chosen, attention should be paid to the factors that ensure high technological and economic efficiency of vitrification. The study of vitrified LILW from the Kursk nuclear power plant with high-power channel reactors (HPCR; equivalent Russian acronym, RBMK) and the Kalinin nuclear power plant with pressurized water reactors (PWR; equivalent Russian acronym VVER) after their 14-yr storage in the shallow-seated repository at the MosNPO Radon testing ground has confirmed the safety of repositories ensured by confinement properties of borosilicate matrix. The most efficient vitrification technology is based on cold crucible induction melting. If the content of a chemical element in waste exceeds its solubility in glass, a crystalline phase is formed in the course of vitrification, so that the glass ceramics become a matrix for such waste. Vitrified waste with high Fe; Na and Al; Na, Fe, and Al; Na and B is characterized. The composition of frit and its proportion to waste depends on waste composition. This procedure requires careful laboratory testing.     

In situ determination of long-term basaltic glass dissolution in the unsaturated zone

Maximum in situ weathering rates of basaltic glass measured at the El Malpais National Monument in New Mexico are on the order of 2–5×10⁻¹⁹ mol/cm² s. Rates were calculated from backscattered electron (BSE) imaging of weathered porosity and are equivalent to 1.7–5% of the surface per 1000 years. Weathering is independent of glass composition but appears to increase with flow elevation at El Malpais. Measured rates represent weathering over 3000 years and are substantially lower than glass dissolution rates measured in the laboratory over much shorter time spans. Basaltic glass is a close chemical analogue to glass hosts proposed for encapsulation of high-level nuclear wastes. Radionuclide release rates predicted from the basis of in situ field rates are substantially less than those predicted from short-term laboratory experiments.     

The geochemistry and provenance of Apollo 16 mafic glasses

The regolith of the Apollo 16 lunar landing site is composed mainly of feldspathic lithologies but mafic lithologies are also present. A large proportion of the mafic material occurs as glass. We determined the major element composition of 280 mafic glasses (>10 wt% FeO) from six different Apollo 16 soil samples. A small proportion (5%) of the glasses are of volcanic origin with picritic compositions. Most, however, are of impact origin. Approximately half of the mafic impact glasses are of basaltic composition and half are of noritic composition with high concentrations of incompatible elements. A small fraction have compositions consistent with impact mixtures of mare material and material of the feldspathic highlands. On the basis of major-element chemistry, we identified six mafic glass groups: VLT picritic glass, low-Ti basaltic glass, high-Ti basaltic glass, high-Al basaltic glass, KREEPy glass, and basaltic-andesite glass. These glass groups encompass 60% of the total mafic glasses studied. Trace-element analyses by secondary ion mass spectroscopy for representative examples of each glass group (31 total analyses) support the major-element classifications and groupings. The lack of basaltic glass in Apollo 16 ancient regolith breccias, which provide snapshots of the Apollo 16 soil just after the infall of Imbrium ejecta, leads us to infer that most (if not all) of the basaltic glass was emplaced as ejecta from small- or moderate-sized impacts into the maria surrounding the Apollo 16 site after the Imbrium impact. The high-Ti basaltic glasses likely represent a new type of basalt from Mare Tranquillitatis, whereas the low-Ti and high-Al basaltic glasses possibly represent the composition of the basalts in Mare Nectaris. Both the low-Ti and high-Al basaltic glasses are enriched in light-REEs, which hints at the presence of a KREEP-bearing source region beneath Mare Nectaris. The basaltic andesite glasses have compositions that are siliceous, ferroan, alkali-rich, and moderately titaniferous; they are unlike any previously recognized lunar lithology or glass group. Their likely provenance is within the Procellarum KREEP Terrane, but they are not found within the Apollo 16 ancient regolith breccias and therefore were likely deposited at the Apollo 16 site post-Imbrium. The basaltic-andesite glasses are the most ferroan variety of KREEP yet discovered.     

Dolomite effect on borosilicate glass alteration

Dolomite (CaMg(CO₃)₂) is one of the common rock-forming minerals in many geological media, in particular in clayey layers that are currently considered as potential host formations for a deep radioactive waste disposal facility. Magnesium in solution is one of the elements known to potentially enhance the alteration of nuclear glasses. The alteration of borosilicate glasses with dolomite as a Mg-bearing mineral source was investigated for 8 months in batch tests at 90 °C. Glass composition effects were investigated through two compositions (SiBNaAlCaZrO and SiBNaAlZrO) differing in their Ca content. The Ca-rich glass alteration is slightly enhanced in the presence of dolomite compared to the alteration observed in pure water. This greater alteration is explained by the precipitation of Mg silicate phases on the dolomite and glass surfaces. In contrast, the Ca-free glass alteration decreases in the presence of dolomite compared to the alteration observed in pure water. This behavior is explained by Ca incorporation in the amorphous layer (formed during glass alteration) coming from dolomite dissolution. Calcium acts as a layer reorganizer and limits glass alteration by reducing the diffusion of reactive species through the altered layer. Modeling was performed using the GRAAL model implemented within the CHESS/HYTEC geochemical code to discriminate and interpret the mechanisms involved in glass/dolomite interactions. Magnesium released by dolomite dissolution reacts with silica provided by glass alteration to form Mg silicates. This reaction leads to a pH decrease. The main mechanism controlling glass alteration is the ability of dolomite to dissolve. During the experiment the quantities of secondary phases formed were very small, but for longer time scales, this mechanism could supply sufficient Mg in solution to form large amounts of Mg silicates and sustain glass alteration. The ability of the GRAAL model to reproduce the concentrations of elements in solution and solid phases regardless of the amount of dolomite and the glass composition strongly supports the basic modeling hypothesis.     

The chemical composition including the Rare Earth Elements of the three major glass types of Europe and the Orient used in late antiquity and the Middle Ages

Sets of 20 soda ash glasses, 16 soda lime glasses and 23 wood ash glasses mainly from excavations in Europe (additional soda ash glasses from Egypt) were analysed on 61 chemical elements. Average SiO₂ is about 62% in soda glasses and 50% in wood ash glasses. The three groups of glasses contain on average 13% Na₂O, 18% Na₂O and 13% K₂O as fluxes to lower the melting temperature of quartz at their production. The starting materials beside quartz were halophytic plant ash for soda ash glass, trona (Na₃H(CO₃)₂·2H₂O) and lime (clamshells) for soda lime glass and beech ash for wood ash glass. Each of the three major glass types contains specific Rare Earth Element (REE) concentrations mainly contained in quartz and its intergrown minerals. 50 Paleozoic and Mesozoic sandstones from Central Europe represent the quartz composition. The REE pattern of these glasses apparently indicates major compositional stages of the Continental Earth's Crust. The boron to lithium and sodium to potassium ratios as in seawater suggest reactions of materials for soda glass with seawater. Negative Ce anomalies in the three glasses are caused by reactions of quartz with seawater.     

Experimente zum Einfluß des Gesteinsglas-Chemismus auf die Zeolithbildung durch hydrothermale Umwandlung

In the formation of zeolites by hydrothermal alteration volcanic glasses are the starting material in most cases. The experiments aimed at demonstrating in what way the chemistry of the volcanic glass influences:

1. the alteration rate of the volcanic glass to zeolites,
2. the kind of zeolites being formed and their formation conditions.

Three volcanic glasses were used, a basaltic, a phonolitic, and a rhyolitic one. The experimental conditions were as similar as possible to the natural alteration conditions. Solutions being used: H₂O dist (pH ～5.5), 0.01 n NaOH (pH ～10.5), and solutions of similar chemistry to the natural ones. The temperatures were 180 °, 200 °, 250 ° C. The experiments were carried out both in closed and in open systems. The experimental results show a difference in the alteration rate and in the zeolites being formed between the basaltic and the phonolitic glasses on the one hand and the rhyolitic one on the other. In case of the closed system the SiO₂-poor volcanic glasses react more rapidly than the SiO₂-rich one. The zeolites being formed are chabazite, phillipsite, analcime respectively mordenite, analcime. In case of the open system the influence of the chemistry of the volcanic glass on the alteration rate and the zeolite being formed is less significant. Which zeolite is formed at a given temperature depends on: the chemistry of the starting material, the chemistry of the reacting solution and wether there is a closed or an open system.     

The dissolution rates of natural glasses as a function of their composition at pH 4 and 10.6, and temperatures from 25 to 74°C

Far-from-equilibrium dissolution rates of a suite of volcanic glasses that range from basaltic to rhyolitic in composition were measured in mixed flow reactors at pH 4 and 10.6, and temperatures from 25 to 74°C. Experiments performed on glasses of similar composition suggest that dissolution rates are more closely proportional to geometric surface areas than their BET surface areas. Measured geometric surface area normalized dissolution rates (r_+,geo) at 25°C were found to vary exponentially with the silica content of the glasses. For pH 4 solutions this relation is given by:

(A1)     

CO2, 13C/12C and H2O variability in natural basaltic glasses: a study comparing stepped heating and ftir spectroscopic techniques

A comparison of two independent techniques was used to assess the homogeneity of CO₂ and H₂O concentrations in a number of natural basaltic glasses. Variations in carbon concentration and isotopic ratio were determined by comparison of stepped heating data obtained in two different laboratories. Dissolved volatile concentrations were also obtained by stepped heating and Fourier Transform Infrared (FTIR) spectroscopy. Replicate stepped heating analyses of a mid-ocean ridge basaltic glass show that the concentration and ¹³C/¹²C of bulk magmatic and dissolved CO₂ vary by less than ±10% and ±0.5‰, respectively. A similar degree of correlation is observed for replicate stepped heating analyses of Mariana Trough glasses conducted in two different laboratories. Dissolved CO₂ concentrations determined by stepped heating also correlate well with concentrations measured by FTIR spectroscopy. The correspondence of results obtained in these experiments provide an upper limit to the degree of natural variation in concentrations and isotopic ratios of these volatiles in basaltic glasses and suggest that intrinsic, magmatic carbon has a relatively homogeneous distribution in these glasses. Water concentrations determined through extraction by heating and FTIR also show excellent agreement.     

A natural analogue of nuclear waste glass in compacted bentonite

A marine based argillaceous rock containing volcanic glass shards has been investigated to infer the long-term durability of vitrified nuclear waste in compacted bentonite, which is a candidate for buffer material constituting the engineered barrier system for nuclear waste disposal. Fission track ages indicate that the volcanic glass shards, andesitic scoria, have been buried in the argillaceous rock for about 1 Ma. Neither glass matrix dissolution nor precipitation on the surface was seen under an optical microscope. Little leaching of any element has been recognized by analyses using an electron microprobe analyzer. Secondary ion mass spectrometry analysis, however, indicates significant hydration which may dominantly be a permeation of molecular water.As an indicator of durability of glass against groundwater a normalized mass loss of Si (NL_Si) has been evaluated for the volcanic glass based on free energy for hydration. The difference between estimated NL_Si of the volcanic glass and that of a simulated waste glass is within one order so that the volcanic glass may be analogous to a waste glass with respect to durability to water. The argillaceous rock is analogous to the compacted bentonite with respect to physical properties such as dry-density, unconfined compression strength, porosity, and hydraulic conductivity. The ambient physical and chemical conditions surrounding the volcanic glass have been also investigated: temperature was in the range from 4 to 30°C due to the burial history of the volcanic glass. Over most of the past 1 Ma the volcanic glass has been in contact with groundwater originating from seawater. Thermodynamic calculations indicate (1) pH (=7.74–7.94) of the groundwater has mainly been controlled by dissolution of carbonate minerals, (2) the redox potential (Eh=−34–−73 mV) of the groundwater has dominantly been controlled by decomposition of organic materials to produce CH₄(g), and (3) activity of aqueous silica of the groundwater was in equilibrium with SiO₂ amorphous. Because of the equilibrium between aqueous silica and SiO₂ amorphous, the volcanic glass did not dissolve during the burial.Vitrified nuclear waste sealed in compacted bentonite, therefore, will not dissolve significantly if buried in an environment as mentioned above.