Microanalysis of colloids and suspended particles from nuclear waste glass alteration

Fully radioactive and non-radioactive Savannah River Laboratory (SRL) borosilicate glasses were reacted with water under static conditions at glass surface area to leachant volume (S/V) ratios of 340 m⁻¹, 2000 m⁻¹, and 20 000 m⁻¹ for times varying from several days to several years at 90°C. A radioactive SRL 200 glass was also reacted under intermittent flow conditions at 90°C. Colloidal and suspended glass alteration particles present in the leachates of these tests were examined with analytical transmission electron microscopy (AEM). The major colloidal phase identified in all tests was partially crystalline dioctahedral smectite clay. At 20 000 m⁻¹, the clay colloids flocculate and sediment, becoming attached to available surfaces when the ionic strength reached a value of about 0.3–0.5 mol·kg⁻¹. Clay colloids remained stable in the solution for the duration of the experiment in tests conducted at S/V values of 2000 m⁻¹ and 340 m⁻¹. Calcite, dolomite, and transition metal oxide particles were more common in the intermittent flow tests but were also found in the static tests. Layered, Mn-bearing minerals, birnessite and asbolane, were found exclusively in the intermittent flow tests. Weeksite and a U-Ti phase were found exclusively in the static tests. Partially crystalline rare earth-bearing calcium phosphate colloids, structurally related to rhabdophane, were found in both types of tests. These particles exhibited a negative Ce anomaly. The affinity of phosphate for Pu was investigated through geochemical modeling. The results from this study and others were used to form a picture of colloidal development in the leachate from waste glass testing.     

Impact of iron on nuclear glass alteration in geological repository conditions: A multiscale approach

Interactions between nuclear glass and Fe were investigated in a clayey environment to better understand the mechanisms and driving forces controlling the long-term behavior of high-level waste glass in a geological repository. An integrated experiment involving a Glass–Iron–Clay (GIC) stack was run at a laboratory scale in anoxic conditions for 2 years and the interfaces were characterized by a multiscale approach using scanning electron microscopy coupled with energy dispersive spectroscopy, transmission electron microscopy, Raman microspectroscopy and scanning transmission X-ray microscopy at the SLS Synchrotron. The characterization of glass alteration patterns on cross sections revealed an increase in glass alteration with the Fe content and the proximity between the glass and Fe. The alteration layers are polyphase and stratified with an inner porous gel layer incorporating Fe and an outer layer composed of nanocrystalline Fe-silicates. Several mechanisms which could affect the glass alteration kinetics and the transport properties of the alteration layer are proposed to explain this pattern: (i) consumption of hydrolyzed silica by precipitation of Fe-silicates; (ii) penetration of Fe within the gel porosity probably as precipitates such as Fe oxyhydroxide or Fe-silicates. These new data may imply some consequences when considering the long-term behavior of glass in geological disposal conditions.     

Presumed magnetic biosignatures observed in magnetite derived from abiotic reductive alteration of nanogoethite

The oriented chains of nanoscale Fe-oxide particles produced by magnetotactic bacteria are a striking example of biomineralization. Several distinguishing features of magnetite particles that comprise bacterial magnetosomes have been proposed to collectively constitute a biosignature of magnetotactic bacteria (Thomas-Keprta et al., 2001). These features include high crystallinity, chemical purity, a single-domain magnetic structure, well-defined crystal morphology, and arrangement of particles in chain structures. Here, we show that magnetite derived from the inorganic breakdown of nanocrystalline goethite exhibits magnetic properties and morphologies remarkably similar to those of biogenic magnetite from magnetosomes. During heating in reducing conditions, oriented nanogoethite aggregates undergo dehydroxylation and transform into stoichiometric magnetite. We demonstrate that highly crystalline single-domain magnetite with euhedral grain morphologies produced abiogenically from goethite meets several of the biogenicity criteria commonly used for the identi?cation of magnetofossils. Furthermore, the suboxic conditions necessary for magnetofossil preservation in sediments are conducive to the reductive alteration of nanogoethite, as well as the preservation of detrital magnetite originally formed from goethite. The findings of this study have potential implications for the identification of biogenic magnetite, particularly in older sediments where diagenesis commonly disrupts the chain structure of magnetosomes. Our results indicate that isolated magnetofossils cannot be positively distinguished from inorganic magnetite on the basis of their magnetic properties and morphology, and that intact chain structures remain the only reliable distinguishing feature of fossil magnetosomes.     

Use of orthophosphate complexing agents to investigate mechanisms limiting the alteration kinetics of French SON 68 nuclear glass

This investigation was carried out to assess the protective properties of the alteration film that develops during aqueous alteration of the French SON 68 (R7T7-type) nuclear glass, notably by examining the behavior of some network-forming cations in the presence of complexing anions. Glass alteration was studied here in the presence of orthophosphate ions. Comparisons were established between two series of tests performed with a solution containing orthophosphate ions and control tests performed under the same conditions but without phosphates. The first series of experiments was performed under initial rate conditions (i.e. in dilute media) to assess the effect of pH and phosphate concentration on the initial glass dissolution rate. Under these conditions, which ensure maximum chemical affinity of the glass dissolution reaction, phosphate adsorption occurs at the reaction interface only with acid pH values, at which the glass dissolution reaction is strongly inhibited. The elements that form complexes with the phosphates (Al, Fe, etc.) partially control glass dissolution in acidic media. Additional experiments carried out under saturated conditions — notably with respect to Si — in a solution enriched with phosphates showed that rare earth and Ca phosphates precipitated in the outer region of the alteration film, maintaining a glass dissolution rate significantly higher than in the control experiment. These observations have several implications. (1) Comparing the results obtained in the presence of phosphates and in the reference medium, the authors demonstrate deductively that glass dissolution is limited by the inner portion of the alteration film, i.e. the amorphous gel. (2) A kinetic law of SON 68 glass dissolution cannot be based on silica alone; the results of these experiments contradict Grambow’s model. (3) With regard to control of the glass dissolution kinetics by the protective properties of the gel, this type of experiment shows that the relation between the chemical composition and the microstructure of the gel is an important aspect in modeling the glass alteration kinetics, but that it is still poorly understood.     

Reactive transport benchmark of MoMaS

We present here the definition of the reactive transport benchmark of Groupement Mathematical Modeling and Numerical Simulation for Nuclear Waste Management Problems. The aim of this benchmark is to propose a challenging test for numerical methods used for reactive transport modeling in porous media. In order to focus on numerical methods, the problem presented here is of quite a small size, both from a hydrodynamical and from a geochemical point of view. Though the chemical coefficients used in this benchmark are not taken from a real chemical system, they are realistic, and the test case is quite challenging.     

Molecular-scale surface processes during the growth of calcite in the presence of manganese

This paper deals with the growth behaviour of the Mn-Ca-CO₃-H₂O solid solution-aqueous solution system on calcite {104} surfaces. This system represents a model example, which allows us to study the effect of a number of controlling factors on the crystallisation: (1) the supersaturation function, β(x), and nucleation rate function, J(x), for the Mn-Ca-CO₃-H₂O system, (2) the relationship of such functions to the molecular scale growth mechanisms operating on growing surfaces, and (3) the surface structure of the calcite {104} faces. In situ atomic force microscopy (AFM) growth experiments revealed a wide variety of surface phenomena, such as the transition between growth mechanisms, anisotropic changes in the step rates, and the influence of the Mn-bearing newly formed surface on subsequent growth (step stoppage followed by the formation of two-dimensional nuclei and the reproduction of the original calcite {104} surface microtopography). These phenomena result from the interplay between the controlling parameters and are explained in those terms.     

Geochronology and stable isotope signature of alteration related to hydrothermal magnetite ores in Central Anatolia,Turkey

Hydrothermal iron ores at Divri?i, east Central Anatolia, are contained in two orebodies, the magnetite-rich A-kafa and the limonitic B-kafa (resources of 133.8 Mt with 56% Fe and 0.5% Cu). The magnetite ores are hosted in serpentinites of the Divri?i ophiolite at the contact with plutons of the Murmano complex. Hydrothermal biotite from the Divri?i A-kafa yield identical weighted mean plateau ages of 73.75?±?0.62 and 74.34?±?0.83 Ma (2σ). This biotite represents a late alteration phase, and its age is a minimum age for the magnetite ore. Similar magnetite ores occur at Hasançelebi and Karakuz, south of Divri?i. There, the iron ores are hosted in volcanic or subvolcanic rocks, respectively, and are associated with a voluminous scapolite ± amphibole ± biotite alteration. At Hasançelebi, biotite is intergrown with parts of the magnetite, and both minerals formed coevally. The weighted mean plateau ages of hydrothermal biotite of 73.43?±?0.41 and 74.92?±?0.39 Ma (2σ), therefore, represent mineralization ages. Hydrothermal biotite from a vein cutting the scapolitized host rocks south of the Hasançelebi prospect has a weighted mean plateau age of 73.12?±?0.75 Ma (2σ). This age, together with the two biotite ages from the Hasançelebi ores, constrains the minimum age of the volcanic host rocks, syenitic porphyry dikes therein, and the scapolite alteration affecting both rock types. Pyrite and calcite also represent late hydrothermal stages in all of these magnetite deposits. The sulfur isotope composition of pyrite between 11.5 and 17.4‰ δ³⁴S_(VCDT) points towards a non-magmatic sulfur source of probably evaporitic origin. Calcite from the Divri?i deposit has δ¹⁸O_(VSMOV) values between +15.1 and +26.5‰ and δ¹³C_(VPDB) values between ?2.5 and +2.0‰, which are compatible with an involvement of modified marine evaporitic fluids during the late hydrothermal stages, assuming calcite formation temperatures of about 300°C. The presence of evaporite-derived brines also during the early stages is corroborated by the pre-magnetite scapolite alteration at Divri?i, and Hasançelebi-Karakuz, and with paleogeographic and paleoclimatic reconstructions. The data are compatible with a previously proposed genetic model for the Divri?i deposit in which hydrothermal fluids leach and redistribute iron from ophiolitic rocks concomitant with the cooling of the nearby plutons.     

Importance of volcanic glass alteration to sediment stabilization: offshore Japan

A minor amount (ca 1 wt%) of amorphous silica cement sourced from volcanic glass inhibits consolidation of hemipelagic sediment approaching the Nankai Trough subduction zone throughout the Shikoku Basin. The distribution and nature of the cement were examined via secondary and backscattered electron imaging. The amorphous silica occurs as altered material in contact with volcanic glass, coating grains (including grain contacts) and filling pores. Based on chemical and petrographic evidence, the cement is probably sourced from volcanic glass; this is in contrast to a previous suggestion that this silica cement is sourced dominantly from biogenic silica. Amorphous silica sourced from disseminated volcanic glass shards has the ability to form a thin coating on clay‐dominated sediment throughout the Shikoku Basin. Measured amorphous silica content in hemipelagic sediments suggests that the cementing process is active throughout the Shikoku Basin (at sites separated by >500 km). The cementation process may occur in other locations where sediment containing hydrated disseminated volcanic glass is buried sufficiently for heat to facilitate alteration (i.e. Central America, Cascadia and the Gulf of Alaska).     

Finite-element method in modeling geologic transport processes

Deterministic mathematical modeling of complex geologic transport processes may require the use of odd boundary shapes, time dependency, and two or three dimensions. Under these circumstances the governing transport equations must be solved by numerical methods. For a number of transport phenomena a general form of the convective-dispersion equation can be employed. The solution of this equation for complicated problems can be solved readily by the finite-element method. Using quadrilateral isoparametric elements or triangular elements and a computational algorithm based on Galerkin's procedure, solutions to unsteady heat flux from a dike and seawater intrusion in an aquifer have been obtained. These examples illustrate that the finite-element numerical procedure is well suited for solving boundary-value problems resulting from modeling of complex physical phenomena.     

Influence of glass composition and alteration solution on leached silicate glass structure: A solid-state NMR investigation

A multinuclear solid-state NMR investigation of the structure of the amorphous alteration products (so called gels) that form during the aqueous alteration of silicate glasses is reported. The studied glass compositions are of increasing complexity, with addition of aluminum, calcium, and zirconium to a sodium borosilicate glass. Two series of gels were obtained, in acidic and in basic solutions, and were analyzed using ¹H, ²⁹Si, and ²⁷Al MAS NMR spectroscopy. Advanced NMR techniques have been employed such as ¹H-²⁹Si and ¹H-²⁷Al cross-polarization (CP) MAS NMR, ¹H double quantum (DQ) MAS NMR and ²⁷Al multiple quantum (MQ) MAS NMR. Under acidic conditions, ²⁹Si CP MAS NMR data show that the repolymerized silicate networks have similar configuration. Zirconium as a second nearest neighbor increases the ²⁹Si isotropic chemical shift. The gel porosity is influenced by the pristine glass composition, modifying the silicon-proton interactions. From ¹H DQ and ¹H-²⁹Si CP MAS NMR experiments, it was possible to discriminate between silanol groups (isolated or not) and physisorbed molecular water near Si (Q²), Si (Q³), and Si (Q⁴) sites, as well as to gain insight into the hydrogen-bonding interaction and the mobility of the proton species. These experiments were also carried out on heated samples (180 °C) to evidence hydrogen bonds between hydroxyl groups on molecular water. Alteration in basic media resulted in a gel structure that is more dependent on the initial glass composition. ²⁷Al MQMAS NMR data revealed an exchange of charge compensating cations of the [AlO₄]⁻ groups during glass alteration. ¹H-²⁷Al CP MAS NMR data provide information about the proximities of these two nuclei and two aluminum environments have been distinguished. The availability of these new structural data should provide a better understanding of the impact of glass composition on the gel structure depending on the nature of the alteration solution.     

The nature of grain boundaries in slates implications for mass transport processes during low temperature metamorphism

The structure of grain boundaries in some very low-grade slates has been studied with transmission electron microscopy. All phyllosilicate boundaries have structural widths of less than 1 nm. A range of structural types have been observed from apparently coherent basal layer chlorite-muscovite boundaries, semi-coherent chlorite-chlorite boundaries and incoherent boundaries which are commonly defined by a thin layer, 7–10 nm thick, of crystalline second phase. Remnants of isolated fluid inclusions are only found at quartz-quartz boundaries. The cleavage microstructures suggest that a large amount of volume loss occurred during cleavage development at low temperatures. This is most likely to have been achieved by diffusion and/or advection through a fluid-filled network present along grain boundaries or grain edges. The phyllosilicate grain boundaries in their present state could not have acted as the pathways for extensive fluid-assisted mass transport. This suggests that the grain boundary structure during cleavage formation was different from the present state. An interconnected fluid network may be maintained along grain boundaries during deformation by hydrofracturing or by grain boundary migration during dehydration reactions, but as deformation and reactions cease the grain boundaries develop an equilibrium structure with very narrow structural widths and restricted fluid distribution.     

Oxidation of magnetite concentrate powders during storage and drying

Oxidation of magnetite pellet concentrates (from LKAB, Sweden) during drying and storage was studied using thermogravimetric analysis (TGA). The Fe²⁺content of a standard LKAB pellet feed decreased by 0.2% during heat treatment at 105 °C for 2 days. The results indicate that magnetite concentrates of pelletizing fineness already start to oxidize to γ-hematite during drying at 105 °C, although 105 °C is recommended by ISO 7764 and ISO 3087 and given as the maximum allowable drying temperature in ISO 3082. The importance of drying time for the amount of magnetite oxidized should also be recognized, but is not mentioned in the ISO standards. The sensitivity of magnetite particles for oxidation during drying could not be predicted by measuring the BET surface area. A simple isothermal TGA run gives exact experimental data and is recommended as a standard procedure before choosing the drying temperature for magnetite concentrate samples.Oxidation during storage at room temperature was observed as well. The Fe²⁺content in a standard Luossavaara-Kiirunavaara (LKAB) pellet feed decreased by 0.3% Fe²⁺during 4 years of storage at room temperature. Oxidation during storage was completely hindered when the samples were stored in a freezer at −50 °C. Therefore, freezer storage is recommended for all magnetite reference materials. These materials are used over several years and are especially susceptible to oxidation because they are usually finely ground and high in Fe²⁺content. The results also show that if the magnetite sample has partly oxidized to γ-hematite, the oxidation curve obtained by TGA will overestimate the Fe²⁺content of the sample, if background correction is necessary.     

Trace element mobility during sub-seafloor alteration of basaltic glass from Ocean Drilling Program site 953 (off Gran Canaria)

Trace element concentrations of altered basaltic glass shards (layer silicates) and zeolites in volcaniclastic sediments drilled in the volcanic apron northeast of Gran Canaria during Ocean Drilling Program (ODP) leg 157 document variable element mobilities during low-temperature alteration processes in a marine environment. Clay minerals (saponite, montmorillonite, smectite) replacing volcanic glass particles are enriched in transition metals and rare earth elements (REE). The degree of retention of REE within the alteration products of the basaltic glass is correlated with the field strength of the cations. The high field-strength elements are preferentially retained or enriched in the alteration products by sorption through clay minerals. Most trace elements are enriched in a boundary layer close to the interface mineral-altered glass. This boundary layer has a key function for the physico-chemical conditions of the subsequent alteration process by providing a large reactive surface and by lowering the fluid permeability. The release of most elements is buffered by incorporation into secondary precipitates (sodium-rich zeolites, phillipsite, Fe- and Mn-oxides) as shown by calculated distribution coefficients between altered glasses and authigenic minerals. Chemical fluxes change from an open to a closed system behavior during prograde low-temperature alteration of volcaniclastic sediments with no significant trace metal flux from the sediment to the water column.     

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.     

Upscaling local-scale transport processes in large-scale relief dynamics

The objective of this paper is to discuss the form and parameters of the macroscopic continent-scale erosion law. The law comes from a spatial integration of local transport processes on the resulting topography. It thus depends on the relief/drainage organization that results from the development of geomorphic instabilities such as differential incisions.Assuming local transport processes to depend on local slope and water discharge, we have calculated topographic evolution to derive the characteristic time scales of erosion dynamics. We especially focused on the case of a declining plateau which presents two main phases: a first phase when the drainage pattern establishes, and a declining phase when topography decreases almost exponentially in the absence of tectonic input. The latter phase is characterized by a time scale which depends on the system size, on the organization of the drainage network, and on the parameters of the transport process. We show that the macroscopic erosion law has the characteristics of an abnormal diffusion whose basic time-length exponent a is determined by the parameters of the fluvial process. This result sheds new light on the observed negative correlation between current denudation rates and drainage areas in world-wide fluvial watersheds.     

Modelling of rock alteration due to coupled heat and mass transport

 A three-dimensional computer model is presented for studying the interaction of heat and mass transport regarding the temporal and spatial evolution of sandstones. The model simulates coupled heat and reactive mass transport in porous rocks. In general, mineral solubilities in water are low. Therefore, large fluid volumes are required to flow through the rock to explain observed mineral cements in sandstones. Besides mass transport, pore fluids transport heat which modifies rock temperatures. Very high flow rates result in strong temperature modifications and, therefore, enhance diagenesis. Low flow rates often cannot account for observed cementation. The model results show the effect of advective, convective and conductive heat transport on temperature and diagenetic evolution of sandstones for two different flow systems in a simple geological environment. Received: 6 August 1996/Accepted: 18 December 1996     

河北省木吉村铜(钼)矿床蚀变分带过程中元素迁移定量分析

为了研究木吉村斑岩型铜(钼)矿床蚀变过程中元素的迁移规律,拟推流体演化规律,笔者通过对赋矿闪长玢岩体的强硅化带、钾长石化带、石英绢云母化带、青磐岩化带中分别取样测试分析,利用Grant方程定量探讨了各蚀变带围岩中主量元素、稀土元素和微量元素的带入、带出特征,结果表明:岩浆初始热液流体富K而贫Na。相对原岩(蚀变弱的青磐岩化带),在各蚀变带中Fe_2O_3、MgO、P_2O_5和TiO_2从深部强硅化带到浅部石英绢云母化带总体上由带出变为带入,SiO_2、MnO则与上述大体相反,FeO在各蚀变带主体为带出元素。各稀土元素从深部向浅部石英绢云母化带带入特征明显,同时各蚀变带在稀土元素球粒陨石标准化曲线上表现出斜率一致的右倾型特征,说明轻重稀土分馏较明显,轻稀土富集,重稀土亏损。Cu和Mo在石英绢云母化带中富集尤为明显,其次在钾长石化带也明显富集,即海拔400~500 m为主要的Cu、Mo富集区。     

Near hydrothermal alteration of obsidian glass: Implications for long term performance assessments

Obsidian glass alteration experiments under near hydrothermal conditions were performed to study mechanism and conditions of formation of altered minerals. X-ray diffraction patterns and cell dimensions of the specimens treated at 150, 200 and 300°C (pH = 8.03) revealed appearance of three main minerals — illite (9.5–10 Å), chlorite (7.04 Å) and halloysite (10.25Å). Further increase in the pH favours matrix dissolution with the formation of secondary altered layers. SEM-EDS study show that the alteration causes smoothing of the grain surfaces. These surfaces exhibits etch pits and series of depressions, formed by the process of dissolution. SEM — Back Scattered Electron images of obsidian specimens show thin laminae of smectite, with foliated bulky rims and cellular honeycomb texture, formed by precipitation from the solution as well as by direct transformation of glass during alteration. This mechanism is resulting from the alteration of alkalis by ionic inter-diffusion with H₃O⁺ and H⁺ and inward diffusion of H₂O, leading to free diffusion of silica into solution and then to a local rearrangement of the glass framework. Thus, a direct transformation of glass into clay minerals is the major reaction mechanism as evidenced by the mechanism of glass dissolution and subsequent mineral precipitation.