A regularly interstratified chlorite/vermiculite occurs in red beds of the East Berlin Formation (Early Jurassic age) in the Connecticut Valley. The mineral is restricted to a 2.5-m wide zone of contact metamorphosed strata adjacent to and underlying the Hampden Basalt. Chemical and X-ray powder diffraction data indicate that the chlorite/vermiculite formed in response to lava-induced elevated temperatures and the availability of magnesium in the muds during and shortly after emplacement of the lava flow. Near the contact, hydrothermal fluids originating from the lava and from the synchronal weathering of basalt fragments by superheated pore waters provided a source of Mg. Further from the contact, magnesium was primarily derived from the thermal dissociation of dolomite. K2O concentrations and the distribution of clay minerals in the red mudstone suggest that the interstratified chlorite/vermiculite formed from preexisting illite or vermiculite as potassium was released and brucitic sheets were incorporated into interlayer positions.

The effects of hydrothermal conditions on the sorption and fixation of cesium by various clay minerals and shales were investigated. Hydrothermal heating, which may be expected in a radioactive waste repository, altered the clay minerals and shales and led to a decrease in their cation-exchange capacity. Cesium sorption greatly decreased in micaceous vermiculite and in well-crystallized illites containing vermiculite upon hydrothermal treatment at 400°C and 300 bars pressure due to complete layer collapse. However, poorly crystallized illites heated as above showed either a small increase or only a slight decrease in Cs sorption because of partial layer collapse. These studies show that the decrease in Cs sorption is greater in well-crysallized illites than in poorly crystallized illites when treated similarly under hydrothermal conditions. Hydrothermal heating of Cs-sorbed and Cs-saturated samples increased the amount of Cs fixation in all minerals and shales as a result of collapse of the layers. For example, a sample of the Conasauga shale fixed only 18% of sorbed Cs before treatment but fixed 47% after hydrothermal treatment at 200°C and 300 bars pressure. Thus, hydrothermal conditions in a shale repository may be beneficial after leaked radioactive Cs ions are taken up by clay minerals in shales.

Hydrothermal alteration products of serpentinite near Takovo, Yugoslavia, were studied by X-ray powder diffraction and chemical analysis. A zone of mainly blue clays adjacent to the hydrothermal vein contains intimately associated chromium kaolinite and tosudite at higher hypsometric levels and chromium halloysite(10Å) form at lower levels. A second zone of green clays contains principally illite/smectites, with predominantly illite layers nearer the first zone and smectite layers at greater distances. The potassium content diminishes as the proportion of illite layers diminishes. The composition of the smectite layers in the illite/smectite with the least proportion of illite is shown to be beidellitic. The mineralogical and chemical changes across the zone of alteration are interpreted in terms of two stages of alteration in which the second is more acidic than the first and is responsible for the inner zone of chromium-bearing kaolinite and tosudite and chromium halloysite.

Several dioctahedral clay minerals are related through reaction series. These series can be produced hydro-thermally from beidellite gel and montmorillonite by making simple changes in interlayer and solution chemistry. The series are:

• gel-K-beidellite-random illite/smectite-K-rectorite-illite

• K-montmorillonite-K-rectorite-illite

• Na-montmorillonite or beidellite-Na-rectorite-paragonite

• Li-montmorillonite-Li-tosudite-Li-rectorite-cookeite(?)

• Mg-montmorillonite-Mg-rectorite-tosudite-sudoite(?)

• Ca-montmorillonite-Ca-rectorite-margarite(?)

• Al-Ca-montmorillonite-kaolinite/smectite-kaolinite (150°C)

• Al-Ca-montmorillonite-pyrophyllite/smectite-pyrophyllite (320°C).

Assuming stability for the mixed-layer phases, paragenesis is a function of P, T, and X conditions. If the phases are considered to be metastable, paragenesis is a function of the speed and path of reaction.

Mixed-layer illite/smectite (I/S) was formed by reacting the Chambers or Polkville montmorillonite hydrothermally at 270° and 350°C from several hours to more than 15 weeks. Reactions were conducted in closed vessels containing K or mixed K-Na, K-Ca, or K-Mg solutions of varying concentrations. The reaction rate and the rate of ordering of I/S for the reaction smectite + K+ → mixed-layer I/S + SiO2 was inhibited by the addition of Na+ Ca2+, and Mg2+; the inhibitory strength of Na+, Ca2+ and Mg2+, on an equivalent basis, increased approximately in the ratio 1:10:30. The first order reaction-rate constants for the reactions at 270° and 350°C indicate an activation energy of about 30 kcal/mole.

In the experimental system studied, the reaction smectite → mixed-layer I/S appeared to proceed by solid state transformation, as suggested by: (1) rapid dissolution of large amounts of silica, probably creating an Al-enriched residue; (2) similarity of particle size and morphology of the mixed-layer products to those of the original montmorillonite, implying no extensive dissolution of Al3+; and (3) relatively high activation energy compared to published values for silicate dissolution.

Kaolinite is synthesized in approximately the same time in three temperature ranges: (1) from 200–250° to 350–400° (hydrothermal processes); (2) from 120 to 175° (semihydrothermal ones); (3) at ordinary temperature. It is thus evident that the rate process cannot be explained by the Arrhenius equation only, but is explained well by considering that kaolinite formation obeys the laws of crystal growth. It occurs only in slightly supersaturated solutions in which the nucleation process is possible and in which a slow and regular rate of growth has been insured. Concentrations calculated from the thermodynamical equilibria correspond to those of the experimental conditions for the low temperature processes. For the higher temperature ones, a similar relationship is delineated, at least as far as the thermodynamical treatment can be carried out.

The immobilization of soluble Cs from spent fuel elements by ion exchange and direct chemical reaction with clay minerals or shales was investigated under hydrothermal conditions. Various clay minerals or shales were reacted with likely Cs sources and water at 300 bars pressure and 100°, 200°, and 300°C for 4, 2, and 1 months, respectively. Pollucite was the principal product, but CsAlSiO4 was also observed, along with unreacted or hydrothermally altered aluminosilicates. From Cs concentrations of the product solutions partition of Cs between liquid and solids was found to vary depending on the Cs source, the clay or shale phase, temperature, and run duration. For example, illite-Cs2MoO4 interactions resulted in 19, 32, and 95% fixation of added Cs at 100°, 200°, and 300°C respectively. Fixation of as much as 97% of the Cs in some solids was observed. In addition to Cs-aluminosilicates, Cs was fixed on cation-exchange sites by interlayer collapse in montmorillonite. Reactions with Cs2MoO4 also produced powellite because Ca was available in the reaction mixture. The U6+ from β-Cs2U2O7 was reduced to form uraninite by sulfide- and/or organic-rich shales. (Cs,Na)2(UO2)(Si2O5)3·4H2O, an analog of weeksite, was produced in reactions with β-Cs2U2O7. The reaction products pollucite and uraninite can immobilize much of the Cs and U from spent fuel elements because Cs in pollucite is extremely difficult to exchange and U in uraninite is insoluble.

The crystallization of calcium zeolites was carried out in an open hydrothermal system at 100°–250°C, using reactants that in nature are known to alter to calcium zeolites and 0.1 N CaCl2, 0.01 N CaCl2, and 0.01 N CaCl2 + 0.01 N NaOH (1:1) solutions. The following calcium zeolites were identified by X-ray powder diffraction:

• Rhyolitic glass: heulandite, phillipsite, epistilbite, wairakite;

• Basaltic glass: phillipsite, scolecite, wairakite, levynite;

• Nepheline: thomsonite, wairakite, gismondine;

• Oligoclase: heulandite, phillipsite, wairakite.

Factors that influenced the type of zeolite formed were: Si/Al ratio of the starting material, calcium/alkali ratio of the starting material, calcium activity of the reacting solution, presence of an open alteration system, and temperature. The Si/Al ratio of the starting material was of special importance in that zeolites formed with Si/Al ratios similar to or smaller than that of the parent material. The calcium/alkali ratio of the starting material also influenced the kind of the early alteration products in the open system. As alteration progressed, the importance of the starting material decreased. The importance of the calcium activity of the reacting solution and the influence of the open system increased as alteration proceeded. Because of mass transfer during alteration in the open system, the calcium content of the minerals formed increased, while their Si/Al ratio decreased. Temperature was especially effective during prolonged alteration, in that the higher the alteration temperature the smaller was the H2O content of the alteration product. Initially, H2O-rich zeolites formed transitorily at higher temperatures.

From hydrothermal experiments three pressure-temperature-time curves have been refined for the system Al2O3−SiO2−H2O and reversal temperatures established for two of the principal reactions involving kaolinite. The temperatures of three isobaric invariant points enable the Gibbs free energy of formation of diaspore and pyrophyllite to be refined and the stability field of kaolinite to be calculated. The maximal temperature of stable kaolinite decreases from 296°C at 2 kb water pressure to 284°C at water's liquid/vapor pressure, and decreases rapidly at lower pressures. On an isobaric plot of [H4SiO4] vs. °K-1, kaolinite has a wedge-shaped stability field which broadens toward lower temperature to include much of the [H4SiO4] range of near-surface environments. If [H4SiO4] is above kaolinite's stability field and the temperature is < 100°C, halloysite forms rather than pyrophyllite, an uncommon pedogenic mineral. Pyrophyllite forms readily instead of kaolinite above 150°C if [H4SiO4] is controlled by cristobalite or noncrystalline silica.

Kaolinite and a common precursor, halloysite, are characteristic products of weathering and hydro-thermal alteration. In sediments, relatively little halloysite has survived due to its low dehydration temperature and instability at low water pressure, but kaolinite commonly has survived since the Devonian Period. In buried sediments, the water pressure and [H4SiO4] requisite for stable kaolinite generally are maintained. In oxidized sediments and in pyritic reduced sediments, kaolinite commonly has survived, but where alkalies, alkaline earths, or aqueous iron has concentrated in the pore fluid, kaolinite has tended to transform to illite, zeolites, berthierine, or other minerals.

A series of hydrothermal experiments was performed to determine the effect of fluid abundance on the reaction of smectite to illite. Experiments were conducted on K-saturated montmorillonite (<0.1-µm fraction) in a closed system at 250° to 400°C using run times of 1, 7, 14, 30, and 60 days at 100 MPa (1 kbar) pressure. In fluid-deficient systems (pore spaces not saturated), the rate and extent of illitization was significantly inhibited. A rock: water ratio of 20:1 (mass: mass) produced an R0 illite/smectite (I/S) having 82% smectite layers after 60 days at 250°C, whereas a rock: water ratio of 1:1 produced an I/S having 57% smectite layers under the same conditions. The effect became less pronounced at higher temperatures, with the 20:1 and the 1:1 experimental products differing by only 11% expandability at 400°C after 60 days. In addition, the low-fluid experiments produced fewer crystalline byproducts (quartz, cristobalite, chlorite) than did the fluid-rich runs, and the I/S was more difficult to disperse and orient in the fluid-deficient samples, suggesting enhanced cementation at grain contacts or the production of particle morphologies that did not lend themselves to orientation. The difference in reactivity of the smectite and I/S as a function of water content appears to be attributable to the reduced capacity for low volumes of water to mediate the dissolution, solute transport, and precipitation reactions that make up the series of reactions collectively termed illitization. Of these variables, solute transport is likely to be affected most by reduction of fluid.

Clay minerals and zeolites, candidate backfill minerals for nuclear waste repositories, were treated with saturated NaCl brine and Mg-rich (Mg-Ca-Na-K) brine at 200°C and 300°C for 4 weeks under a confining pressure of 30 MPa. The Al concentrations released in NaCl brine were lower than those in Mg-rich brine at both temperatures indicating that the Mg-rich brine is more acidic than the NaCl brine under these hydrothermal conditions. The Si concentrations in both brines were low because of the relatively acidic conditions developed during the hydrothermal treatment. As determined by X-ray powder diffraction or by specific Cs and Sr sorption measurements, no alteration could be detected in clay minerals treated with NaCl brine at 200°C. Among the zeolites tested, only phillipsite and erionite altered to analcime in NaCl brine at 200°C. Zeolites and most of the clay minerals tested did not alter in the Mg-rich brine treated at 200°C. Vermiculite altered to randomly interstratified vermiculite/K-vermiculite (mica-like) by selective K uptake from the Mg-rich brine.

At 300°C, the clay minerals did not greatly alter, whereas the zeolites altered to analcime and/or albite in the presence of the NaCl brine. In the Mg-rich brine, Al-rich montmorillonite from Wyoming did not alter, whereas Al-poor montmorillonite from Texas altered to randomly interstratified montmorillonite/ illite at 300°C. Vermiculite collapsed to form K-vermiculite (~ 10.2 Å) by the selective uptake of K from the Mg-rich brine at 300°C. Most of the zeolites altered to smectites in the Mg-rich brine at 300°C because of the acidic conditions generated by the hydrolysis of Mg. The selective Cs-sorption Kd decreased from 11,700 for untreated phillipsite to 240 and 15 for the hydrothermally produced analcime/albite mixtures from the phillipsite at 200° and 300°C, respectively, in NaCl brine. These results suggest that montmorillonites and mordenites are relatively more resistant than vermiculite or other zeolites at elevated temperatures and pressures in concentrated hydrothermal brines expected in a salt repository.

Point defect centers in hydrothermal kaolinite have been investigated using electron paramagnetic resonance (EPR). Kaolinite was sampled in petrographically well-defined materials coming from uranium-rich hydrothermally altered volcanic tuffs (Nopal I uranium deposit, Chihuahua, Mexico), which show extensive kaolinization and an intense redistribution of uranium. Several kaolinite parageneses were defined according to their origin (fissure fillings and feldspar pseudomorphs); their location relative to the U6+ mineralization at the scale of the deposit (mineralized breccia pipe vs. barren surrounding rhyolitic tuffs), and at the scale of mineral assemblages; and their crystal chemistry.

Two types of centers of axial symmetry were identified (A- and A′-centers) and represent positive holes trapped on apical oxygens (Si-O−-centers). A-centers were stable to 400°C, whereas A′-centers annealed at 350°C. A relation between defect-center concentration and U content demonstrates that natural irradiation was responsible for these centers. On the other hand, defect-center concentration was not directly linked to the origin (fissural or feldspar pseudomorph) or the crystal chemistry (structural order and substitutional Fe3+ content) of the kaolinite. According to petrographic data, and with respect to the relative thermal stability of A- and A′-centers, two successive irradiations of kaolinite were evidenced: (1) originally during crystallization of kaolinite from radioactive hydrothermal solutions, and (2) permanently when kaolinite was in contact with secondary U-silicates, which led to the formation of A′-centers.

Because of the short half-life of U, these two radiation-induced centers were created by short-lived elements of the U-decay series. As a consequence, variations of defect-center concentration possibly reflect variations in radioactive disequilibrium during the history of the alteration system. This provides a unique tool for tracing the dynamics of the transfer of radionuclides in the geosphere: kaolinite may be used as a sensitive in situ dosimeter, which may be useful in the fields of weathering petrology and nuclear waste management.

Published chemical data for suites of mixed-layer minerals from diagenetic sedimentary rocks, hydrothermally altered tufts, and a metasomatic bentonite bed indicate that the layer charge and composition of the different components of illite/smectite (I/S) differ from one geological environment to another. It appears that the composition of the elemental smectite and illite layers in the I/S is more or less constant for samples within each geologic setting. In the examples considered, the smectite layers are predominantly montmorillonitic in character (i.e., the charge is in the octahedral site), whereas the illite layers show different types of charge sites, depending upon the suite studied. Illite layers appear to have about the same charge in all three suites studied, slightly more than 0.7 per O10(OH)2 unit, whereas the smectite layers in the different suites range in charge from about 0.3 to 0.7 per O10(OH)2 unit. Cation-exchange capacities reflect these differences in charge, although not ideally. The differences in the composition of the component layers in each geologic suite of mixed-layer clays are probably due either to differences in the bulk chemistry of the rocks in the different suites or to differences in intensive variables, such as temperature and pressure, of the regime under which they have formed.

The amount of K fixed in K- and Ca-saturated montmorillonite, vermiculite (trioctahedral), rectorite-type and IMII-ordered mica/montmorillonites was measured as a function of time (1–64 days), temperature (25o-300°C), pH (6.0, 9.7, and 10.7), and K-concentration (0.02 and 1.0 M) in solution. The amount of K fixed by the clays generally increased with increasing temperature, pH, and K-concentration and reached saturation in response to each experimental condition in 5 or 6 days. The K-montmorillonite and K-vermiculite fixed considerable amounts of K even at 25°C. Fixed K in montmorillonite increased with an increase of the layer charge which is also influenced significantly by the interlayer cation. In detail, the behavior in K-fixation was specific to each clay.

The type of structural transformation with K-fixation was different for each clay. In montmorillonite, especially, the type of transformation was related to the cationic composition of the system; in K homoionic system, montmorillonite transformed rapidly into illite/montmorillonite with about 40% expandable layers at 300°C and in a mixed cation system with Ca and K, it reacted gradually to random illite/montmorillonites with increasing temperature. These data indicate that the cation-exchange process of a natural pore solution plays an important role in the gradual transformation of detrital montmorillonite to illite.

Investigations were conducted to determine the hydrothermal transformations of synthetic birnessite exchanged with different metal ions. Autoclaving in a Teflon-lined stainless steel pressure vessel at 155°C for 24 hr of Mg-, Ca-, La-, and Co-saturated birnessite yielded manganese minerals having 10-Å X-ray powder diffraction (XRD) spacings. The autoclaved Mg-birnessite yielded a mineral identical to natural todorokite in its infrared (IR) spectrum and XRD patterns. High-resolution transmission electron microscopy (HRTEM) provided images having 10-, 12.5-, 15-, and 20-Å wide fringes indicating heterogeneous channel widths in the crystallographic a direction, and IR spectroscopy produced bands at 757, 635, 552, 515, 460, and 435 cm-1, confirming the product obtained by autoclaving Mg-birnessite to be todorokite. Prolonged autoclaving of Mg-birnessite yielded manganite (γ-MnOOH) as a by-product; manganite did not form when the autoclaving time was shortened to 8 hr. Also, when Ca-saturated samples were autoclaved, the product gave d-values of 10 Å, but the XRD lines were broad and heterogeneity of the channel sizes was evident from HRTEM observations. The Ca-derivative had an IR spectrum similar to that of natural todorokite. Images showing 10-Å lattice fringes were observed by HRTEM for the Ni-saturated sample, which also produced an XRD pattern similar to that of the Mg-saturated sample. Co- and Lasaturated samples did not form todorokite, although HRTEM of La-saturated samples indicated some 10-Å lattice fringes that were unstable in the electron beam. Birnessite saturated with Na, K, NH4, Cs, Ba, or Mn(II) gave products having 7-Å spacings upon autoclaving.

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.