Radium sorption efficiencies as a function of temperature, Ra concentration, and secondary mineral sorbate were determined in a 0.01 M NaCl solution. Radium sorption on a characterized clinoptilolite, montmorillonite, nontronite, opal, silica gel, illite, kaolinite, and glauconite under comparable experimental conditions allowed determination of Ra sorption efficiency curves for each, through use of Freundlich constants, over the same temperature and initial Ra solution concentration range. Similar sorption data for U on the same secondary minerals over the same temperatures allowed comparison of sorption efficiencies for Ra and U. Clinoptilolite, illite, and nontronite were the most efficient Ra sorbents, while opal and silica gel were the poorest Ra sorbents. Generally, Ra sorption on secondary minerals was much greater than U sorption under the same experimental conditions.

Well-characterized American Petroleum Institute clay standards, source clays from The Clay Minerals Society, and other secondary minerals were used to determine the effects of U concentration, temperature, and solution composition on U-sorption properties. Uranium concentrations ranged from about 1.00 × 10−4 M to 4.00 × 10−7 M, temperatures from 5° to 65°C and solution compositions containing 0.01 M NaCl and 0.01 M NaHCO3. Silica gel efficiently sorbed uranyl carbonate anion complexes. The higher cation-exchange capacity materials most readily sorbed uranyl ions from the 0.01 M NaCl solution. Temperature increases tended to affect uranyl ion sorption adversely except when the U was present as carbonate complexes. Noncrystalline ferric oxyhydroxides sorbed uranyl ions much more efficiently than any of the secondary crystalline minerals studied. A method for accurately extrapolating U-sorption efficiencies between experimental points based on the Freundlich equation is presented.

In an attempt to resolve the structure of opal-CT and opal-C more precisely, 24 opal samples from bentonites, Fuller's Earths, zeolite tuffs, biogenic silicas and silicified kaolins have been analyzed by high resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD). Results of this examination demonstrate that opal-C and opal-CT are part of a continuous series of intergrowths between end-member cristobalite and tridymite stacking sequences.

These findings are consistent with Flörke's (1955) interpretation of the most intense opal peak at ~4 Å as a combination of the (101) cristobalite and (404) tridymite peaks. The position and width of this peak are controlled by the relative volume of the two stacking types and the mean crystallite size. Direct evidence obtained by HRTEM provides data showing various stacking sequences in opals. Broadening due to crystallite size alone was determined by directly measuring crystallite size by TEM and comparing the measured size to the apparent size calculated using the Scherrer equation. XRD peak broadening is also described in terms of various contributions from structural disorder. The mean opal crystallite size ranges from 120 to 320 Å. For samples at either end of the size range, the crystallite size plays a larger role, relative to stacking disorder, in controlling peak broadening.

A siliceous sinter collected from Octopus Spring in Yellowstone National Park, USA contains an occluded volcanic rock fragment that has undergone alteration. The sinter piece beyond the fragment is mostly dominated by opal-A with trace amounts of bacterial cells, calcite and detrital quartz. Within the altered rock region, the mineral assemblage is dominated by dioctahedral smectite and quartz with trace amounts of pseudobrookite, ilmenite, rutile and hematite. Onset of opal-CT formation was only found in the outer spicular region of the sinter, which is unexpected given that this outer part represents newest growth. A reaction mechanism is proposed whereby the alteration of feldspar to smectitic clay locally produces excess silica, and alkali metal, and raises pH. As the clay mineral forms, it sequesters ions from pore fluids thereby inhibiting the opal-A phase change to more ordered opal-CT. Ions such as Mg are known to promote the opal-A to opal-CT reaction. Smectite formation therefore may assist microbial-texture preservation processes as excess silica produced increases the rate at which primary opal-A is formed. The altered zone also retains the greatest amount of fixed C and fixed N (operationally defined as C and N retained upon combustion at 450°C). The fixed N probably represents ammonium trapped in the exchangeable interlayer site of the smectite. This fixed N may serve as a potential biological signature of microbial activity in ancient rocks formed in similar environments.

Layers of volcanic ash and Andosol soils derived from the ash may play an important role in preserving snow and ice as well as in the development of permafrost conditions in (a) the immediate vicinity of volcanoes at high elevations or at high latitudes and (b) land areas that are often distant from volcanic activity and are either prone to permafrost or covered by snow and ice, but have been affected by subaerial ash deposition. The special properties of volcanic ash are critically reviewed, particularly in relation to recent research in Kamchatka in the Far East of Russia. Of special importance are the thermal properties, the unfrozen water contents of ash layers, and the rate of volcanic glass weathering.Weathering of volcanic glass results in the development of amorphous clay minerals (e.g. allophane, opal, palagonite), but occurs at a much slower rate under cold compared to warm climate conditions. Existing data reveal (1) a strong correlation between the thermal conductivity, the water/ice content, and the mineralogy of the weathered part of the volcanic ash, (2) that an increase in the amounts of amorphous clay minerals (allophane, palagonite) increases the proportion of unfrozen water and decreases the thermal conductivity, and (3) that amorphous silica does not alter to halloysite or other clay minerals, even in the Early Pleistocene age (Kamchatka) volcanic ashes or in the Miocene and Pliocene deposits of Antarctica due to the cold temperatures. The significance of these findings are discussed in relation to past climate reconstruction and the influence of volcanic ash on permafrost aggradation and degradation, snow and ice ablation, and the development of glaciers.

Indurated volcanic soils (tepetates) of the Mexican Altiplano display thick columnar horizons, hard laminar horizons, and grey mottles at depth. X-ray diffraction (XRD) studies show a relative enrichment in cristobalite vs. halloysite in the indurated plates of the laminar horizons and in the clay fraction of the mottles. Transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) studies of these two soil components have shown that they are composed of small tubes of halloysite in which numerous globular grains ∼1 μm in diameter are embedded. Based on the relative abundance of cristobalite in pedological features and on the spatial relations between successive mineral phases, we interpret the cristobalite as a transformation of halloysite with a transitional amorphous phase. In the globular grains, large platy 1:1 clay minerals undergo a progressive transformation into platy particles of opal-A and opal-C. These are in turn transformed into cristobalite without further major change in their shape and appearance, except for a higher electron density than opal and clay.

Laser Raman spectroscopy is particularly well suited for routine characterization of the crystalline and the better ordered paracrystalline silica phases occurring in silica sinters: opal-C, quartz and moganite. The non-crystalline and poorly ordered paracrystalline silica phases (opal-CT and opal-A) are identified with difficulty, partly as a result of the high level of fluorescence exhibited by the younger sinters that are dominated by these phases, and partly as a result of the ill-defined nature of the broad phonon scattering bands produced by them. Nonetheless, given the limited number of phases present and the high level of phonon scattering from the better ordered phases, judicious use of a Raman microprobe enables the character of most siliceous microtextural sinter components to be determined readily. Microprobe examination of a series of New Zealand sinters, ranging from Late Quaternary to Pliocene in age shows that a silica phase inhomogeneity that exists in some outcrops reflects an underlying phase heterogeneity obtaining in the microstructure of the sinter; it is a consequence of the phase transformation process. In the older sinters, quartz, moganite and opaline cristobalite may be present in a single fabric element but in quite different proportions to their abundance in adjacent elements. Identification of opaline lepispheres partially pseudomorphed by quartz+moganite and the association of quartz+moganite in microcrystals exhibiting common quartz forms, cautions against the use of morphology as a means of identifying silica phases at the microstructural level.

We have carried out TEM observations of agates of geode origin and Beltane opals. Optically observable individual fibres in agates are composed of many fine fibres which consist of quartz crystallites of 8 to 100 nm in length stacked together parallel to <110> or <100> with c-axes perpendicular to the fibre elongation. The optically observable systematic striations in agate are found to consist of cyclic alternation of layers due to variation in grain size and porosity. Large quartz crystals, protruding into the spaces of geodes, represent the last stage of formation of these bands, and are merely a continuation of the banding sequence. Nanometre scale textures of cristobalite fibres were revealed in Beltane opals. The cristobalite crystallites have the size of 3 to 20 nm in length and are also stacked together. Our TEM results suggest that embryonic particles were formed in their corresponding growth environments and agglutinated to form fibres.

The nature of the alteration of basaltic, andesitic and rhyolitic glass of Holocene and Pleistocene age and their physical and chemical environments have been investigated in the ash layers within the cryogenic soils associated with the volcanoes in the central depression of Kamchatka. One of the main factors controlling the alteration of the volcanic glass is their initial chemistry with those of andesitic (SiO2 = 53–65 wt.%) and basaltic (SiO2 < 53 wt.%) compositions being characterized by the presence of allophane, whereas volcanic glass of rhyolitic composition (SiO2>65 wt.%) are characterized by opal. Variations in the age of eruption of individual ashes, the amount and nature of the soil water, the depth of the active annual freeze-thawing layer, the thermal conductivity of the weathering soils, do not play a controlling role in the type of weathering products of the ashes but may affect their rates of alteration.