The cooling of steel containers in radioactive-waste storage was simulated in a step-by-step experiment from 90 to 40ºC. Among newly formed clay minerals observed in run products, cronstedtite was identified by a number of analytical techniques (powder X-ray diffraction, transmission electron microscopy, and scanning electron microscopy). Cronstedtite has not previously been recognized to be so abundant and so well crystallized in an iron—clay interaction experiment. The supersaturation of experimental solutions with respect to cronstedtite was due to the availability of Fe and Si in solution, as a result of the dissolution of iron metal powder, quartz, and minor amounts of other silicates. Cronstedtite crystals are characterized by various morphologies: pyramidal (truncated or not) with a triangular base and conical with a rounded or hexagonal cross-section. The pyramidal crystals occur more frequently and their polytypes (2M1, 1M, 3T) were identified by selected area electron diffraction patterns and by automated diffraction tomography. Cronstedtite is stable within the 90-60ºC temperature range. At temperatures of ⩽ 50ºC, the cronstedite crystals showed evidence of alteration.

Dioctahedral vermiculite commonly occurs in soils and fresh sediments, but has not been reported in sedimentary rocks. Little is known of the evolution of this mineral during diagenesis. According to the available literature, dioctahedral vermiculite is likely to exhibit strong potential for selective sorption and fixation of K+ involving interlayer dehydration and collapse. he objective of the present study was to investigate the influence of K+ saturation and seawater treatments on the structure o dioctahedral vermiculite. Due to the fact that no dioctahedral vermiculite standard reference material was available, a natural sample of soil clay containing dioctahedral vermiculite was used in the study. The clay was saturated with K+ using different protocols simulating natural processes taking place in soils and marine environments. The solid products of the experiments were analyzed for potassium content using flame photometry. The effect of the treatments used on the structure of dioctahedral vermiculite was studied using X-ray diffraction (XRD). The percentages of the collapsed interlayers were estimated by modeling the XRD patterns based on a whole-pattern multi-specimen modeling technique. All the treatments involving K+ saturation caused K+ fixation and irreversible collapse (i.e. contraction to 10 Å) of at least a portion of the hydrated (vermiculitic) interlayers. Air drying of the K+-saturated samples greatly enhanced the degree of the collapse. The results obtained gave no clear answer as to whether time had had a significant effect on the degree to which irreversible collapse occurred. Selective sorption of K+ from artificial seawater was observed. These results clearly indicate that collapse of dioctahedral vermiculite is likely to occur in soils during weathering and in sediments during early diagenesis. Both processes need to be taken into consideration in sedimentary basin studies.

Pedogenic smectite from a young (Holocene) tropical soil was reacted in Al-rich solution at 150ºC for a range of reaction times (3 to 120 days) in orderto study mechanisms and rates associated with the transformation of smectite to kaolinite via interstratified kaolinite-smectite (K-S). As has been observed in tropical soils, the overall reaction rate is logarithmic, with rapid initial transformation of smectite to K-S with ~50% smectite layers, followed by progressively slower transformation of intermediate K-S to kaolinite-rich K-S and eventually Fe-kaolinite. Sub-micron hexagonal non-Fe-bearing kaolinite forms in the final stage (after 120 days) as a minor mineral in an assemblage dominated by Fe-kaolinite. The pedogenic smectite used as starting material consisted of two end-members, Fe-beidellite and Al-smectite, enabling comparison of reaction pathways. Fe-beidellite transforms to K-S or Fe-kaolinite within 3 days, whereas Al-smectite transforms much more slowly, appearing to reach a maximum rate in intermediate stages. This difference is probably due to hydrolysis of relatively weak Mg-O and Fe-O bonds (relative to Al-O bonds) in Fe-beidellite octahedral sheets, which drives rapid reaction, whereas the driving force behind transformation of Al-smectite is more likely to be related to stripping of tetrahedral sheets which reaches its maximum rate at intermediate stages. Multiple analytical approaches have indicated that Al is rapidly fixed from solution into smectite interlayers within K-S, and that K-S and Fe-kaolinite inherit octahedral Fe and Mg from precursor smectite; as the reaction progresses, octahedral sheets become progressively more Al-rich and Fe and Mg are lost to solution. These results demonstrate that: (1) early-formed pedogenic smectite in tropical soils is expected to transform to kaolinite via interstratified K-S; (2) K-S has a strong potential to sequester plant-toxic Al in tropical soil; and (3) the presence in tropical soils of Fe-kaolinites with relatively large cation exchange capacities may be related to inheritance of octahedral sheets from precursor smectite and K-S.

The delivery of plastic fines such as bentonite into loose saturated granular soil deposits is an effective method for mitigating the liquefaction phenomenon. While the bentonite should be injected into the deposits in the form of a concentrated suspension, such application is limited in practice because of the low mobility of the suspension. The initial mobility of the bentonite suspension should be managed in order to increase the penetration depth. On the other hand, the suspension needs to maintain its thixotropic nature to improve the resistance of the treated soils under cyclic loading over time. The objective of the present study was to investigate the dynamic rheological properties of the bentonite suspensions modified with an ionic additive, sodium pyrophosphate (SPP), to evaluate a possible application of the modified suspensions in mitigation of liquefaction. In the present study, the storage and loss modulus of SPP-modified bentonite suspensions were measured using a strain-sweep (oscillatory shear) technique. Bentonite suspensions with clay contents of 5, 7.5, 10, and 12 wt.% (by total weight of suspension) were tested at various SPP concentrations (0 to 4 wt.% by weight of dry bentonite). The time-dependent behavior of the suspensions was evaluated with a critical storage modulus at various resting times (0 to 480 h). The results showed that the initial critical storage modulus decreased significantly with increasing SPP concentrations, but the reduced critical storage modulus increased gradually with resting times. This initial reduction in critical storage modulus is attributed to a reduction of the inter-aggregated 3-D networks due to the presence of SPP; the amount of 3-D network formed in a suspension governs the critical storage modulus. With time, the networks are formed gradually, resulting in recovery of critical storage modulus. The normalized modulus was degraded more slowly in the modified suspensions than in the unmodified suspensions, which is a desirable property of the suspensions for mitigation of liquefaction.

Bentonite is to be used as a sealing material for long-term storage of radioactive waste. During permafrost periods the buffer may freeze, causing the following: montmorillonite dehydration, ice formation, and pressure build-up that may fracture the surrounding rock. No previous study has been done on freezing of bentonite in saline water. Using small and wide angle X-ray scattering, the present study aimed to increase understanding of the combined impact of salt and temperature on the hydration (swelling) of Wyoming montmorillonite. The basal spacing of the Na-montmorillonite was very dependent on the water content, while this was not the case for the Ca-montmorillonite (after reaching 19 Å). The basal spacing of the free-swelling Na-montmorillonite (34–280 Å) was estimated successfully using simple calculations. During freezing of Na-montmorillonite in NaCl solution, both ice and hydrohalite formed (at -50 and -100ºC). At starting concentrations ≥ 1.5 M the basal spacing was not affected by freezing. During freezing of Ca-montmorillonite in CaCl2 solution, ice formed; antarcticite formed only sporadically. The basal spacing of the Ca-montmorillonite at high NaCl concentrations (>1 M) was greater at -50 and -100ºC (18 Å) than at 20ºC (16 Å). The opposite was observed at low concentrations. This change was attributed to small amounts of salts introduced into the montmorillonite interlayer, hence changing the interlayer water properties. The montmorillonite hydration was also temperature dependent; decreasing temperature increased the hydration (as long as no ice was formed) and increasing the temperature decreased the hydration. This was attributed to the temperature impact on the entropy of the hydration reaction. This observation was also reproduced in an experiment up to 90ºC. A small amount of salt in the groundwater was noted to reduce significantly the potential problem of ice formation in bentonite sealings.

The intercalating growth of new silicate layers or metal hydroxide layers in the interlayer space of other clay minerals is known from various mixed-layer clay minerals such as illite-smectite (I-S), chlorite-vermiculite, and mica-vermiculite. In a recent study, the present authors proposed that smectite-group minerals can be synthesized from solution as new 2:1 silicate layers within the low-charge interlayers of rectorite. That study showed how oxalate catalyzes the crystallization of saponite from a silicate gel at low temperatures (60ºC) and ambient pressure. As an extension of this work the aim of the present study was to test the claim that new 2:1 silicate layers can be synthesized as new intercalating layers in the low-charge interlayers of rectorite and whether oxalate could promote such an intercalation synthesis. Two experiments were conducted at 60ºC and atmospheric pressure. First, disodium oxalate solution was added to a suspension of rectorite in order to investigate the effects that oxalate anions have on the structure of rectorite. In a second experiment, silicate gel of saponitic composition (calculated interlayer charge -0.33 eq/O10(OH)2) was mixed with a suspension of rectorite and incubated in disodium oxalate solution. The synthesis products were extracted after 3 months and analyzed by X-ray diffraction and high-resolution transmission electron microscopy (HRTEM). The treatment of ultrathin sections with octadecylammonium (nC =18) cations revealed the presence of 2:1 layer silicates with different interlayer charges that grew from the silicate gel. The oxalate-promoted nucleation of saponite and talc crystallites on the rectorite led to the alteration and ultimately to the destruction of the rectorite structure. The change was documented in HRTEM lattice-fringe images. The crystallization of new 2:1 layer silicates also occurred within the expandable interlayers of rectorite but not as new 2:1 silicate layers parallel to the previous 2:1 silicate layers. Instead, they grew independently of any orientation predetermined by the rectorite crystal substrate and their crystallization was responsible for the destruction of the rectorite structure.

Desorption processes of low-molecular-weight compounds from the surface of smectites into the gas phase determine a number of processes, e.g. those involved in drug delivery and the release of herbicides. The desorption has not been investigated thoroughly and is not well understood. The present study was undertaken in order to understand better the factors influencing these desorption mechanisms. Starting with a very pure standard (Na+-rich) montmorillonite (Kunipia-F), which was exchanged against cations with different hydration properties (Ca2+, Li+, phenyltrimethylammonium, hexyltrimethyl-ammonium), the experiments explored the rate of desorption of volatiles with different chemical functionalities (water, ethanol, ethyl acetate, and toluene). The desorption was monitored by thermogravimetry and differential scanning calorimetry under isothermal conditions, and by ramping the temperature at a constant rate. The experiments were compared with numerical calculations based on finite-element methods and with analytical models. These data point to a two-step mechanism where the desorption follows the curve of the equilibrium desorption isotherms of those molecules on the montmorillonite. The bulk-like volatiles (i.e. volatiles with release kinetics close to that of the bulk liquids) were desorbed in a first step. With a decrease in the degree of coverage of the volatile on the montmorillonite, the desorption was increasingly dominated by the strength of interaction between the volatile and the interlayer cations of the montmorillonite.

The crystal growth of NH4-illite (NH4-I) from the hydrothermal system of Harghita Bãi (Eastern Carpathians) was deduced from the shapes of crystal thickness distributions (CTDs). The <2 mm and the <2-0.2 mm fractions of clay samples collected from the argillized andesite rocks consist of NH4-illite-smectite (I-S) interstratified structures (R1, R2, and R3-type ordering) with a variable smectite-layer content. The NH4-I-S (40-5% S) structures were identified underground in a hydrothermal breccia structure, whereas the K-I/NH4-I mixtures were found at the deepest level sampled (-110 m). The percentage of smectite interlayers generally decreases with increasing depth in the deposit. This decrease in smectite content is related to the increase in degree of fracturing in the breccia structure and corresponds to a general increase in mean illite crystal thickness. In order to determine the thickness distributions of NH4-I crystals (fundamental illite particles) which make up the NH4-I-S interstratified structures and the NH4-I/K-I mixtures, 27 samples were saturated with Li and aqueous solutions of PVP-10 to remove swelling and then were analyzed by X-ray diffraction. The profiles for the mean crystallite thickness (Tmean) and crystallite thickness distribution (CTD) of NH4-I crystallites were determined by the Bertaut-Warren-Averbach method using the MudMaster computer code. The Tmean of NH4-I from NH4-I-S samples ranges from 3.4 to 7.8 nm. The Tmean measured for the NH4-I/K-I mixture phase ranges from 7.8 nm to 11.7 nm (NH4-I) and from 12.1 to 24.7 nm (K-I).

The CTD shapes of NH4-I fundamental particles are asymptotic and lognormal, whereas illites from NH4-I/K-I mixtures have bimodal shapes related to the presence of two lognormal-like CTDs corresponding to NH4-I and K-I.

The crystal-growth mechanism for NH4-I samples was simulated using the Galoper code. Reaction pathways for NH4-I crystal nucleation and growth could be determined for each sample by plotting their CTD parameters on an α-ß2 diagram constructed using Galoper. This analysis shows that NH4-I crystals underwent simultaneous nucleation and growth, followed by surface-controlled growth without simultaneous nucleation.