Compacted bentonite, used as an engineering barrier for permanent containment of high-level radioactive waste, is susceptible to mineral evolution resulting in compromise of the expected barrier performance due to alkaline–thermal chemical interaction in the near-field. To elucidate the mineral-evolution mechanisms within bentonite and the transformation of the nuclide adsorption properties during that period, experimental evolution of bentonite was conducted in a NaOH solution with a pH of 14 at temperatures ranging from 60 to 120°C. The results showed that temperature significantly affects the stability of minerals in bentonite under alkali conditions. The dissolution rate of fine-grained cristobalite in bentonite exceeds that of smectite, with the phase-transition products of smectite being temperature-dependent. As the temperature rises, smectite experiences a three-stage transformation: initially, at 60°C, the lattice structure thins due to the collapse of the octahedral sheets; at 80°C, the lattice disintegrates and reorganizes into a loose framework akin to albite; and by 100°C, it further reorganizes into a denser framework resembling analcime. The adsorption properties of bentonite exhibit a peak inflection point at 80°C, where the dissolution of the smectite lattice eliminates interlayer pores and exposes numerous polar or negatively charged sites which results in a decrease in specific surface area and an increase in cation exchange capacity and adsorption capacity of Eu3+. This research provides insights into the intricate evolution of bentonite minerals and the associated changes in radionuclide adsorption capacity, contributing to a better understanding of the stability of bentonite barriers and the effective long-term containment of nuclear waste.

Imogolite occurs as tiny bumps less than 0.05 µm in diameter and about 0.3 µm long on amorphous thin layers on the surface of weathered plagioclase. The bumps grow outward from the surface to form projections, which then develop into a fibrous imogolite. The fibers branch out and grow into widespread networks or thin films which finally cover the entire surface of the plagioclase grain. The fibers are about 0.05 µm in diameter as seen by transmission electron microscopy.

To identify mineral alterations which might occur in stream environments, predominantly illitic soil clays were equilibrated in bottom sediment environments under natural and laboratory conditions for 217 and 98 days, respectively. Changes occurring after 217 days on the bottom of the Auglaize River, Ohio, consisted of a reduction in carbonate content, a decrease in particle size, and a slight loss of Al and Si; however, no significant changes in basal spacings were observed.

Clays equilibrated in river water under laboratory conditions at 4° and 25°C in CO2, N2, or air atmospheres showed only an increase in oxalate-extractable iron. The concentrations of Al, Si, Fe, Mn, K, and Ca in solution above the clays varied with the atmosphere and temperature. The concentrations of Fe, Al, and Si in solution may have been influenced by the dissolution of amorphous Al-Fe-Si compounds. Therefore, the mineralogical differences between soils in the watershed and sediments in the drainage system can not be attributed to mineralogical transformations during residence in the drainage system.

Petrographic observations indicate that dolomite, siderite, pyrite, Ti oxides, quartz, and K-feldspar formed as by-products of mica alteration during diagenesis of Jurassic reservoir sandstones of the Haltenbanken area (offshore central Norway). These minerals precipitated on a mica-grain scale or a thin-section scale. Modal analyses and mass-balance calculations of muscovite alteration to kaolinite and of biotite to kaolinite, illite, and chlorite suggest limited elemental mobility during sandstone diagenesis. The alteration of mica to kaolinite occurred in sandstones buried <2200 m deep (present temperature < 70°C), whereas illitization and chloritization of biotite occurred during burial to depths > 3000 m (present temperature >95°C).

Sodium-saturated Wyoming bentonite was hydrothermally reacted at 150° and 250°C for 30 to 180 days to determine smectite alteration rates that might be applied to nuclear-waste repository design. Na-Ca solutions deficient in K were used to determine the role of interlayer cations in the creation of high layer-charge in the smectites. The results provide insight into the mechanism and timing of various steps in the diagenetic alteration of smectite to illite. X-ray powder diffraction (XRD) analyses of the reacted clay showed little effect on the character of the 17-Å reflection even after 180 days at 250°C. Potassium saturation of these reacted clays and re-examination by XRD indicated collapse of some smectite layers, leaving at most only 60% expandable layers. The development of layer charge sufficient to cause collapse on saturation with a low hydration energy exchange-cation does not require K in the reacting fluid. Rate constants for the illitization reactions as determined by K-saturated collapse are between 1.0 × 10−3 and 2.8 × 10−3/day with activation energies <3.5 kcal/mole. Ca in a Na-silicate-bicarbonate solution slightly reduced the illitization rate constants. These rate constants are higher than expected from extrapolation of studies of beidellite-composition glasses at higher temperatures, but lower than values obtained in studies of natural clays in artificial sea water. The release of Si, Al, and Mg in the 150°C experiments suggests congruent dissolution of the smectite. In contrast, at 250°C the release of Al was not stoichiometric with Si; as little as one half of the relative available Si was released. Rather than different mechanisms for dissolution at the two temperatures, the conclusion is that noncrystalline Al-rich phases formed at greater rates at higher temperatures. The cation-exchange capacities for several of these reacted smectites were significantly less than expected, suggesting a clogging of interlayer sites, perhaps by Al-complexes.

The instability of palygorskite and sepiolite under soil conditions was investigated to determine if these fibrous minerals transform directly to smectite under laboratory conditions. The treatment of 100 mg (0.12 mmole) of palygorskite with 1 mmole of NaOH solution (17 ml) at 150°C for 24 hr yielded a smectite. Analcime and smectite were formed when ≥ 3 mmole of NaOH was used. The addition of ≤ 6 mmole NaOH to sepiolite destroyed it gradually. On addition of ≥ 8 mmole NaOH, sepiolite altered to an X-ray amorphous material. In the presence of Al and Si, however, it transformed to smectite and analcime. Transmission electron microscopy, cation-exchange capacity, and X-ray powder diffraction studies of the products suggest that alteration wa. (1) via solution, o. (2) by a structural reorganization wherein the basic 2:1 silicate structural units were unchanged.

Weathered perthite and mixed muscovite-kaolinite from a kaolinitic granite at Trial Hill in east Queensland and kaolinized sericitic alteration from a granite from the Ardlethan Tin Mine of New South Wales were examined by optical, scanning electron (SEM), and transmission electron microscopy (TEM) to determine the alteration process of muscovite to kaolinite and kaolinite to halloysite (7Å). Muscovite was found intimately interleaved with kaolinite in a variety of proportions on a sub-micrometer scale. The contact was generally parallel to the (001) layers of both minerals, and the thickness of the contact layer alternated between 10 and 7 Å over short distances. Where the kaolinite to muscovite contact was at an acute angle to the muscovite layers, a small angle existed between the layering of the two phases, consistent with a topotactic alteration of muscovite to kaolinite. One tetrahedral sheet in the muscovite appeared to have been removed over 50–100 Å, converting a 10-Å layer to a 7-Å layer. The mica near the contact with kaolinite was easily damaged in the electron beam and showed Al loss during analytical transmission electron microscopy; thus, H3O+ probably substituted for K+ in this transitional phase.

An SEM examination of completely weathered plagioclase showed kaolinite plates having attached, parallel, polygonal rods of halloysite (7Å), which had planar sides and a central void, partly fused with the surfaces of the kaolinite crystals. TEM study showed that the kaolinite altered to halloysite, and that, where the kaolinite was partly altered to halloysite, a series of sharp kinks were present in the kaolinite plate in which alteration had occurred. These kinks were interspersed with linear kaolinite relics, 0.1–0.2 μm long, which appear to have provided local rigidity to the clay packet. Apparently, the altered clay first curled into loosely wound spirals, which ranged in cross-section from triangles to irregular octagons, with pentagons and hexagons being most common. The tendency to pentagons and hexagons compares well with a statistical study of the angles, which were most commonly grouped around 120°. As alteration of the kaolinite relics progressed, the linear parts of the spiral lost their rigidity and became circular or oval shaped. The long axis of the halloysite spirals was parallel to the X axis of the kaolinite. Halloysite spirals formed most readily if they had space to curl; if space was not available, the halloysite formed sheaves. Rare, thin layers of muscovite were present projecting through kaolinite into halloysite. Where muscovite relics reached open spaces, the 10-Å structure expanded to 14 Å.

Single crystal X-ray diffraction and electron-optical analysis were used to investigate the weathering of a chromium-bearing muscovite (fuchsite). The muscovite had mostly altered to kaolinite with minor amounts of halloysite occurring between kaolinite plates. Evidence for both epitactic and topotactic growth of kaolinite from muscovite was obtained and no intermediate poorly-crystalline phases were detected. About half of the Cr in fuchsite was incorporated into kaolinite, whereas most of the Ti, Fe and Mg was lost.

The clay mineralogy of an oxisol-saprolite overlying serpentinite and underlying basalt was studied with different techniques to evaluate the clay mineral transformation that occurred and to understand the origin of Fe3+-rich smectite. The saprolite zone of the oxisol, up to 30 m thick, contains smectites of the montmorillonite-beidellite and montmorillonite-nontronite series, as well as illite, chlorite, talc, and goethite or amorphous oxyhydrates. Illite is mainly concentrated in the upper 50 cm thick zone underlying the basalt layer and chlorite-content increases toward altered serpentinite at the base. Minor amounts of nontronite formed mostly toward westward exposures where the hot contact layer between serpentinite and basalt is only 20 cm thick. Greene-Kelly Li-tests revealed that all samples contain montmorillonite, but one sample shows the presence of a minor amount of beidellite.

Parent rocks are a mixture of mainly mica schist (the source of beidellite), and minor serpentinite in different percentages and laterally distributed. These rocks were intensely weathered under humid climatic conditions. Silica was concentrated as amorphous transparent (pure silica) cobbles and milky quartz pebbles, and originated from geothermal solutions rising through the Ovaclk thrust fault. The Mg partly formed chlorite. Ferrian smectites in serpentinites were derived obviously from the Mg-rich minerals but Mg is lost much more rapidly than Si during the formation of the clay deposit. The structural formula of the most Fe-rich smectite samples from the study area is (Si6.60−7.10Al1.40−0.90)(Al2.54−1.22Mg0.32−0.92Fe3+1.18−1.68−Ti0.06−0.04)(Ca0.16−0.10Na0.02K0.02−0.12)O20(OH)4. This composition is within the range recorded for the ferrian montmorillonite-beidellite series, with very little vermiculite forming the oxisol-vertisol horizon.

The alteration experiments of phlogopite with 0.01 N HCl solution containing 0.1 M NaCl at 50°, 80° and 120°C have been carried out to aid in the understanding of the dissolution process of mica and the formation of secondary phases such as vermiculite and interstratified mica/vermiculite. Twenty milligrams of phlogopite samples were suspended in 20 ml or 100 ml of leaching solution.

In these experiments, the dissolution ofphlogopite occurred incongruently, where the preferential release of K occurred in almost all stages of the alteration reaction. In the 100 ml experiments, the priority in dissolution in the initial stage was in the order; K > Fe > Mg, Al > Si. This supports that phlogopite leaching is controlled by the mineral structure. At 80° and 50°C in the 20 ml experiments, the release of all elements except for K was nearly congruent. At 120°C in the 20 ml experiments, the dissolution was outwardly incongruent, which Fe decreased remarkably after six days and Al was released most slowly compared with all other elements in phlogopite. This is probably due to the precipitation of secondary phases such as aluminum and iron oxides and/or hydroxides.

Vermiculite and R1-type interstratified mica/vermiculite, containing 70 ∼ 50% mica, were formed in the alteration process of phlogopite. The following two processes were confirmed for the formation of interstratified structure: Interstratified structure was formed (1) directly from phlogopite or (2) from vermiculite which was produced earlier from phlogopite by regaining of K from the ambient solution. It may depend on the release rate of K from phlogopite whether mica-vermiculite layer sequences develop or vermiculite-vermiculite sequences do.

The structure, chemistry and distribution of hydrothermal alteration and weathering products of feldspars and glass in 3 samples of Yucca Mountain tuffs (GSW G4 borehole at a depth of 1531 ft (464 m) and USW GU3 borehole at 1406 ft (426 m) from the Calico Hills Formation and USW G4 at a depth of 272 ft (82.4 m) from the Topobah Springs Member) were examined by high-resolution transmission electron microscopy (HRTEM) and analytical electron microscopy (AEM). Alteration products are of interest because they may influence the form and distribution of contaminants released from the proposed high-level nuclear waste repository. Samples from the Calico Hills Formation contain alkali-bearing aluminosilicate glass and its alteration products. Zeolites appear to have formed from compositionally similar glass by recrystallization, probably under hydrothermal conditions. Crystals are fibrous and frequently no more than a few tens of nanometers in diameter. Porous aggregates of few-nanometer-diameter, poorly crystalline silica spheres (probably opal C-T) develop adjacent to corroded glass surfaces and zeolite crystals. Finely crystalline Fe-rich smectites coat etched glass surfaces, zeolites and feldspar crystals and occur within opal-like silica aggregates. Microstructures in the clay-dominated coatings and details of smectite-glass interfaces suggest that clays grow in orientations controlled by heterogeneously retreating surfaces and from constituents released at associated glass dissolution sites. The alteration assemblage also includes finely crystalline hematite, goethite, Mn-oxide films and illite formed by alteration of muscovite. The zeolitized sample contains abundant opal-like silica whereas glass in the unzeolitized sample is weathered to smectite-like clays. These differences may be attributed to hydrological and consequent geochemical factors resulting from the higher porosity of zeolitized samples. Exsolved alkali feldspar, which occurs as micron-sized crystals in the Calico Hills Formation and as phenocrysts and in the groundmass of the devitrified Topobah Springs Member, are almost unaltered. Feldspar alteration is confined to cracks and grain boundaries, where minor, poorly crystalline, Fe-bearing aluminosilicate alteration products are developed. In these tuffs, most of the porosity, permeability, high surface area and capacity to affect solution chemistry are associated with products of glass alteration.

Progressive alteration by seawater of an andesite in the Aegean Island of Milos and an ignimbrite in the Aegean Island of Kimolos, Greece, formed bentonites with or without zeolites. Both profiles are dominated by migration of alkalis and uptake of Mg, Fe and H2O, while Al and Ti are immobile. The relative removal of alkalis controls the formation of either smectite or zeolites. The behavior of Ca and Si depends on the chemistry of the parent rock. In the rhyolitic profile, alteration is controlled by gain of Mg, Fe2+ and Ca and loss of Na, K and Si, while in the andesitic profile by gain of Mg and Fe2+ and loss of Na, K and Ca. In both profiles, significant uptake of SO4- was not observed. Moreover Zr, Nb, V and Ni are immobile and have been enriched residually, while Sr, Rb and Y are lost in both profiles. Thorium is immobile in the rhyolitic profile but is leached in the andesitic profile. Also, the rare earth elements (REE) display fractionation in both profiles; the degree of fractionation increases with the degree of alteration to bentonite. Fractionation of the REE in both profiles and mobility of Th in the andesitic profile are related to the existence of monazite (rhyolitic profile) and apatite (andesite profile). The REE and Th appear to partition into phosphates rather than smectite.

The mobility of Y coupled with the immobility of Nb increases the Nb: Y ratio with advancing alteration, rendering discrimination diagrams that use this ratio to determine the nature of the protoliths misleading. Mass balance calculations showed that in the smectite-rich zones the water: rock (WR) ratio might be as high as 13:1 in both profiles, while in the zeolite-bearing zones it is about 5.5:1. Such WR ratios explain the observed extensive mass transfer and suggest that the pore fluid chemistry might overprint the chemical characteristics of the parent rocks controlling smectite and bentonite chemistry.

Magnetic fractionation, chemical, and structural analyses prove that alteration of ilmenite from Manavalakurichi deposit extends only up to the formation of pseudorutile with traces of rutile. The data indicate that ferrous to ferric iron transformation, ferric iron oxide formation, and iron removal contribute to the alteration sequence. The first two highly magnetic fractions are not unaltered ilmenite. A reduction in ilmenite unit cell volume indicates the ferrous-ferric conversion occurred during alteration.

Nacrite and dickite are found in two localities in northern Taiwan. One, containing nacrite and dickite, is associated with a gold-enargite deposit as a vug-filling clay in the Chinkushih (CKS) mine district near the northern coast. The other is the occurrence of dickite in the interstices of a Miocene coarse-grained quartzose sandstone in the Nanshihchiao (NSC) area, near Taipei city. X-ray diffraction (XRD), differential thermal analysis (DTA), scanning electron microscope (SEM), and petrographic examinations were used to characterize the mineralogical features. Nacrite most often takes the unusual form of rhombic platelets, and dickite is commonly elongated in habit with the shapes possibly related to their origin. Based on geological evidence, we believe that both nacrite and dickite are of hydrothermal origin. In the CKS area, the formation of nacrite and dickite is related to the hypogene gold-enargite mineralization. In contrast, the transformation of dickite in the NSC area is due to the influence of the raised temperatures of sandstone formation, resulting from volcanic activity during the Kungkuan stage after the deposition of the sandstone.

Altered perthites from a weathered pegmatite in the Spruce Pine District, North Carolina, were characterized by electron microprobe as a K-rich microcline host with lesser Na-rich plagioclase having a lamellar morphology. Light-optical and transmission electron microscopy (TEM) show microtextural elements such as phase boundaries, holes and microfractures that could serve as potential nucleation sites for alteration to clay minerals.

The host microcline contains albite and pericline twinning textures that vary in character; the amount of each twinning type and/or the size of twin individuals changes on a μm scale. Plagioclase ranges from large lamellar vein and film albite (visible in the light microscope) to cryptoperthite whose size ranges from μm to perhaps 100 Å. The smallest-scale albite appears to be a late-stage phase of exsolution in which lamellae have nucleated heterogeneously on albite-twin composition planes in the microcline.

Alteration is concentrated in vein and film albite, especially along grain boundaries with microcline. Powder X-ray diffraction (XRD) patterns of intensely altered pegmatite show halloysite. Holes, microfractures, vein albite/host microcline boundaries and microcline/halloysite boundaries trend parallel to the traces of (010) and {110}, suggesting that these directions are pathways along which fluids migrate. Cleavage and microfractures occur along, and holes are bounded by, these directions. Holes are associated with dislocations and the latter are observed at feldspar/clay boundaries. Twin domains and cryptoperthitic albite are less susceptible to alteration than coarse lamellar albite and regions containing negative crystals and microfractures. However, microtextures in some areas containing halloysite suggest that once fluids penetrate the crystal, alteration may proceed preferentially in more strongly twinned regions.

The Tazzeka Mountain, located approximately 20 km south of Taza, eastern Morocco, is composed of a Westphalian volcano-sedimentary complex. It contains rhyolitic ignimbrites with the following minerals: quartz, potassium feldspar, oligoclase-andesine, and biotite. The ignimbrites are extensively altered because of a dense network of fractures in the massif. Alteration has resulted in the formation of spheroidal rocks and saprolite, the thickness of which depends on local topography. The evolution of the biotites in the ignimbrites was investigated by microprobe analysis of the mica crystals. This technique provides data that are not accessible through classical analytical methods. Biotites are transformed into secondary clay minerals, mainly chlorites and illites; intermediate stages are related to the degree of alteration of biotite, the latter being expressed by the K2O content which decreases progressively from 7.3 to 1.3%. Next come protochlorites and chlorites sensu stricto, in which the K2O content is 0.3%. Several processes including retrodiagenesis, hydrothermal activity, fumarolic activity, and geochemical weathering contributed to the transformation of the biotites at Tazzeka.

Chlorite and illite are commonly associated with ubiquitous secondary K-rich feldspar in the rocks located immediately above and below the Precambrian-Paleozoic unconformity in southwestern Ontario, and elsewhere in the mid-continent of North America. This alteration assemblage is attributed to long-distance migration of hot brines driven westward by orogenic processes originating along the eastern seaboard of North America. The δD and δ18O values of chlorite and illite, plus K-Ar dates for secondary K-rich feldspar and illite, were used to determine the nature, origin, and timing of the fluids that altered Precambrian granites and their overlying rocks in southwestern Ontario. The δ18O values of the chlorite-forming fluids are best explained by initial hot brines (≥50°C) evolved mostly from seawater. Secondary K-rich feldspar formation followed shortly thereafter, as the fluids cooled and perhaps mixed with meteoric water. Regional migration of the brines was induced by Taconic orogenic events to the east. The hydrogen and oxygen isotopic compositions for the secondary illite of the early to mid-Carboniferous indicate its crystallization from local meteoric water at low temperatures (40–55°C). Infiltration of local meteoric water into the Paleozoic and uppermost altered Precambrian rocks occurred during uplift, erosion, and subaerial exposure of local arches in southern Ontario. The local basement reactivation and associated secondary illite formation in this portion of the North American hinterland was likely a distal expression of east-coast Acadian and Alleghanian orogenic activity.

The weathering of chlorite, one of the major minerals of the host rock in the uranium ore deposit at Koongarra, Australia, was examined by X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), electron microprobe analysis, and transmission electron microscopy (TEM). The conversion sequence of chlorite weathering is: (1) chlorite; (2) chlorite/vermiculite intergrade (showing XRD responses to various treatments intermediate between those of chlorite and vermiculite); (3) interstratified chlorite and vermiculite; (4) vermiculite; and (5) kaolinite. This sequence may be more simply expressed as chlorite ⤒ vermiculite ⤒ kaolinite. The weathering finally changed chlorite into sub-micrometer to micrometer sized Fe minerals and kaolinite. The transformation of chlorite to vermiculite is chemically characterized by an Fe and Mg loss with a slight decrease in the Al/Si ratio. Mg continues to be released throughout the weathering. Fe minerals formed through chlorite weathering are located between chlorite and vermiculite domains (a few μm in size) at first, and then accumulated between grain boundaries, occasionally forming veins. The distribution of Fe minerals is suggestive of preferential pathways of water movement. The time-dependent nature of mineral alteration demonstrated in the present study must be taken into account for the quantitative estimation of radionuclide migration.

Samples of ash layers and associated background sediments from Site 808 of ODP Leg 131 in the Nankai Trough accretionary prism were analyzed for changes in mineralogy, porosity and micro-fabric associated with alteration of volcanic ash. Ash layers range from incipient stages of alteration and dissolution to complete alteration to clay minerals and clinoptilolite. Ash layers contain greater abundances of total clay minerals and lower percentages of quartz than do surrounding background hemipelagic sediments. The clay-sized fraction of ash layers is dominated by pure dioctahedral smectite, whereas the background sediments contain primarily illite and chlorite with minor amounts of smectite. Analysis of microfabric revealed dramatic changes in the distributions and abundances of grains and pores during ash alteration. The relative abundances of large pores, grains, and matrix material were quantified on digital back-scattered electron images (BSEI) of ash layer and background sediment samples. During burial, the abundant glass shards of shallow ash layers are initially altered, presumably to smectite. Subsequent dissolution of the glass leaves open, shard-shaped pores, resulting in increased porosities. With greater burial, these pores are filled with clinoptilolite. Although the presence of ash and its alteration products clearly influences sediment physical properties, there is no apparent correlation of the abundance of ash or its alteration products with the formation of thrust faults or other structures within the Nankai Trough accretionary prism.