Volume 63 - Issue 6 - December 2015
Article
Mineralogical Evolution of Di- and Trioctahedral Smectites in Highly Alkaline Environments
- Kerstin Elert, Eduardo Sebastián Pardo, Carlos Rodriguez-Navarro
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 414-431
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The mineralogical evolution of di- and trioctahedral smectites (i.e. montmorillonite and saponite) exposed to high-pH environments has been studied to determine the influence of compositional differences on clay dissolution and the formation of new phases. The present study helps to gauge the effects of highly alkaline solutions on the swelling capacity of smectitic clays and experimental results are extrapolated to predict the behavior of smectite-rich soils in various technical applications such as nuclear-waste storage and architectural conservation. The present study revealed extensive dissolution of montmorillonite in 5 M NaOH or 5 M KOH solutions and the neoformation of various zeolites, thereby reducing the clay’s swelling capacity significantly. Saponite, in contrast, experienced less pronounced changes, including transformation into a randomly interstratified saponite-chlorite and a Si-rich amorphous phase. These changes only provoked a partial reduction in swelling capacity. The results imply that under repository conditions (e.g. alkaline environment caused by hyperalkaline fluids released during concrete leaching), the slow and limited transformation of saponite into corrensite-type minerals would be beneficial for preserving the clay’s swelling capacity and, therefore, its effectiveness as a sealing material. Conversely, the loss of swelling capacity as a result of zeolite formation in montmorillonite observed in the present experiments would limit the clay’s effectiveness as a sealing material in waste repositories. In the case of earthen architecture conservation, alkaline consolidation treatments aimed at reducing the soils’ swelling capacity and, thereby, improving water resistance, would only be effective for treating earthen structures made of soils rich in dioctahedral smectites. Soils containing trioctahedral smectites, in contrast, are not likely to improve their water resistance because the swelling capacity will only be partially reduced.
Formation and Restacking of Disordered Smectite Osmotic Hydrates
- Benjamin Gilbert, Luis R. Comolli, Ruth M. Tinnacher, Martin Kunz, Jillian F. Banfield
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 432-442
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Clay swelling, an important phenomenon in natural systems, can dramatically affect the properties of soils and sediments. Of particular interest in low-salinity, saturated systems are osmotic hydrates, forms of smectite in which the layer separation greatly exceeds the thickness of a single smectite layer due to the intercalation of water. In situ X-ray diffraction (XRD) studies have shown a strong link between ionic strength and average interlayer spacing in osmotic hydrates but also indicate the presence of structural disorder that has not been fully described. In the present study the structural state of expanded smectite in sodium chloride solutions was investigated by combining very low electron dose, high-resolution cryogenic-transmission electron microscopy observations with XRD experiments. Wyoming smectite (SWy-2) was embedded in vitreous ice to evaluate clay structure in aqua. Lattice-fringe images showed that smectite equilibrated in aqueous, low-ionic-strength solutions, exists as individual smectite layers, osmotic hydrates composed of parallel layers, as well as disordered layer conformations. No evidence was found here for edge-to-sheet attractions, but significant variability in interlayer spacing was observed. Whether this variation could be explained by a dependence of the magnitude of long-range cohesive (van der Waals) forces on the number of layers in a smectite particle was investigated here. Calculations of the Hamaker constant for layer-layer interactions showed that van der Waals forces may span at least five layers plus the intervening water and confirmed that forces vary with layer number. Drying of the disordered osmotic hydrates induced re-aggregation of the smectite to form particles that exhibited coherent scattering domains. Clay disaggregation and restacking may be considered as an example of oriented attachment, with the unusual distinction that it may be cycled repeatedly by changing solution conditions.
Measuring the Layer Charge of Dioctahedral Smectite by O—D Vibrational Spectroscopy
- Artur Kuligiewicz, Arkadiusz Derkowski, Katja Emmerich, George E. Christidis, Constantinos Tsiantos, Vassilis Gionis, Georgios D. Chryssikos
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 443-456
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Layer charge (LC) is a fundamental property of smectite but its measurement remains challenging and tedious to apply on a high-throughput basis. The present study demonstrates that the position of a sharp, high-energy O—D stretching band of adsorbed D2O (νO—D, at ~2686–2700 cm−1), determined by infrared spectroscopy, correlates with LC and provides a simple method for its measurement. Twenty nine natural dioctahedral smectites and 14 reduced-charge montmorillonites with LC determined previously by different methodologies were saturated with D2O and examined by attenuated total reflectance infrared spectroscopy (ATR-IR). The samples included smectites in Mg, Ca, Na, Li, K, and Cs forms and covered the full range of the smectite LC (0.2 to 0.6 e per formula unit). Statistically significant correlations were found between νO—D and LC values determined with each of the two main methods of LC determination: the structural formula method (R2 = 0.96, σ = 0.02, ~0.2 < LC < 0.6) and the alkylammonium method (R2 = 0.92, σ = 0.01, 0.27 < LC < 0.37). These correlations were based on Li- and Na-saturated smectites, respectively, but other cationic forms can be employed provided that the exchangeable cations are of sufficiently high hydration enthalpy (e.g. Mg2+ or Ca2+, but not K+ or Cs+). The new method is fast, low-cost, implemented easily in laboratories equipped with ATR-FTIR, and applicable to samples as small as ~5 mg.
Effect of Surface Charge and Elemental Composition on the Swelling and Delamination of Montmorillonite Nanoclays Using Sedimentation Field-flow Fractionation and Mass Spectroscopy
- Shoeleh Assemi, Sugandha Sharma, Soheyl Tadjiki, Keith Prisbrey, James Ranville, Jan D. Miller
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 457-468
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The swelling properties of smectite-type clay particles (including montmorillonite) are of interest in various industries. A fundamental understanding of the surface properties of smectite particles at the sub-micron level would facilitate investigation of the effect of distributed properties such as charge and elemental composition. Swelling and delamination of SWy-2 Na-montmorillonite (Na-Mnt) nano-clay particles were studied here using size distributions obtained by sedimentation field-flow fractionation (SdFFF). Fractions were examined by electron microscopy and inductively-coupled optical emission spectroscopy (ICP-OES). Two distinct populations were observed in the size distribution of SWy-2 Na-Mnt particles (bimodal size distribution), with mean equivalent spherical diameters of ~60 nm and 250 nm, respectively. In contrast, the size distribution of STx-1 Ca-montmorillonite (Ca-Mnt) particles showed only one peak with a mean equivalent spherical diameter of ~410 nm, which changed to 440 nm after 4 days of hydration. Analyses of the fractions by ICP-OES obtained along the size distribution of Na-Mnt showed an abundance of Ca and Mg in the fractions below 250 nm, and confirmed the presence of Fe and Mg as isomorphous substituents. Electron micrographs of the fractions obtained from Na-Mnt size distributions were used to calculate the thickness of the clay particles. Bridging forces between pure orMgsubstituted montmorillonite and either Ca2+ or Na+ were calculated using semi-empirical methods. The results demonstrated that swelling and delamination of Na-Mnt clay particles are dictated by properties such as elemental composition and surface charge which are distributed along the size distribution.
Diagenetic and Paleoenvironmental Controls on Late Cretaceous Clay Minerals in the Songliao Basin, Northeast China
- Yuan Gao, Chengshan Wang, Zhifei Liu, Xiaojing Du, Daniel E. Ibarra
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- 01 January 2024, pp. 469-484
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Sedimentary and diagenetic processes control the distribution of clay minerals in sedimentary basins, although these processes have seldom been studied continuously in continental sedimentary basins. The Songliao Basin, northeast China, is a large continental, petroleum-bearing basin, and provides a unique study site to understand the sedimentary and diagenetic processes that influence clay assemblages. In this paper, the clay mineralogy of a 2500 m-thick Late Cretaceous (late Turonian to Maastrichtian) terrestrial sedimentary succession (SK-1s and SK-1n cores), retrieved by the International Continental Scientific Drilling Program in the Songliao Basin, was examined. The objective was to determine the diagenetic and paleoenvironmental variations that controlled the formation of clay mineral assemblages, and to determine the thermal and paleoenvironmental evolution of the basin. The results from both cores show that illite is ubiquitous through the succession, smectite is frequently encountered in the upper strata, and ordered mixed-layer illite-smectite (I-S), chlorite, and kaolinite are abundant in the lower strata. Burial diagenesis is the primary control on the observed decrease of smectite and increasing illite, I-S, and chlorite with depth. Observations of clay-mineral diagenesis are used to reconstruct the paleotemperatures and maximum burial depths to which the sediments were subjected. The lowermost sediments could have reached a maximum burial of ~1000 m deeper than today and temperatures ~50°C higher than today in the latest Cretaceous. The transition of smectite to I-S in the SK-1 cores and the inferred paleotemperatures provide new constraints for basin modeling of oil maturation at elevated temperatures in the Songliao Basin. Authigenic kaolinite and smectite are enriched in sandstones with respect to the coeval mudstones from the SK-1n core, as a result of early diagenesis with the participation of primary aluminosilicates and pore fluids. In the upper part of both SK-1 cores, variations in smectite and illite were controlled primarily by paleoenvironmental changes. Increases in smectite and decreases in illite from the late Campanian to Maastrichtian are interpreted as resulting from increasing humidity, a conclusion consistent with previous paleoenvironmental interpretations.
Referees Volume 63
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- Published online by Cambridge University Press:
- 01 January 2024, p. 485
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