Volume 66 - Issue 4 - August 2018
Article
Securing The Future: Clay-Based Solutions For a Comprehensive and Sustainable Potable-Water Supply System
- Giora Rytwo
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 315-328
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Today’s water-treatment plants combine practices designed to cope individually with various types of purification challenges. In some cases, the solution to one has detrimental effects on others, e.g. disinfection by chlorination forming hazardous organic contaminants. Water-treatment plants have large ecological footprints and operational costs, making the availability of high-quality water in developing areas almost impossible, due to lack of resources and infrastructure. Indeed, >2 billion people are exposed to diseases caused by contaminated water. Clearly, bringing safe, clean drinking water to people’s homes is essential to a good quality of life. Clay minerals may offer technologies and innovative practices which would help to develop a reliable, low-maintenance device with a small environmental footprint that processes stream, lake, or pond water into high-quality potable water. The basis for such technologies has already been established and improved approaches are being introduced on an ongoing basis by clay scientists: nanocomposite pre-treatment and disinfection, photodegradation of organic pollutants using clay-based catalysts, polishing of inorganic contaminants, and removal of biological pathogens by adsorption or deactivation onto specifically designed clay-based filters, etc. This short review presents a vision for combining those technologies in a tandem system for the delivery of high-quality water that is low-maintenance, affordable, and environmentally sustainable for the benefit of mankind.
Pore Geometry as a Limiting Factor for Anion Diffusion in Argillaceous Rocks
- C. Wigger, M. Plöze, L. R. Van Loon
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 329-338
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Several barrier types are envisaged to minimize the release of radionuclides from waste matrices into groundwater. In a number of countries argillaceous rocks make up the natural barrier that will isolate radioactive substances from the aquifer. The present study addresses the influence of pore geometry as a limiting factor for anion diffusion in argillaceous rocks. Irrespective of the pore core size, anion diffusion can be limited by the pore-size opening, i.e. if the pore opening is so narrow that the electric double layers overlap and form a barrier to anions irrespective of the pore size. This so-called ‘bottleneck effect’ limits the anion diffusion. The present study extends previous investigations that focused on other factors which limit anion diffusion, e.g. mineralogy or interlayer equivalent pores. The existence of bottleneck pores was confirmed by effective tortuosity calculations and retention-potential measurements using mercury intrusion porosimetry. On the basis of two different core samples from argillaceous rocks from Switzerland, Opalinus Clay and Helvetic Marl, this work shows evidence of the existence of bottleneck pores. The larger permanent anion exclusion in the Helvetic Marl sample compared to the Opalinus Clay sample can be explained by the larger retention potential and larger effective tortuosity of the Helvetic Marl rock, which indicates more pores with bottleneck effects than is the case for the Opalinus Clay rock.
Formation of Arrested States in Natural Di- and Trioctahedral Smectite Dispersions Compared to Those in Synthetic Hectorite — A Macro- and Microrheological Study
- M. Pilavtepe, L. Delavernhe, A. Steudel, R. Schumann, N. Willenbacher, K. Emmerich
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 339-352
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The effect of natural clay-mineral properties on the rheological behavior of dispersion is very important in new geotechnical and industrial applications. The colloidal behavior of natural clay minerals with various octahedral structures was investigated using macro- and microrheological measurements and compared with the behavior of synthetic hectorite. In the present study montmorillonite (dioctahedral smectite of Volclay), natural hectorite (trioctahedral smectite of SHCa-1 Source Clay), and the synthetic trioctahedral smectite Laponite®, with lateral layer dimensions of 277, 100, and 30 nm, respectively, were used. The structure formation, kinetics of aging, and broad bandwidth viscoelastic response (10-2 — 106 rad/s) of their dispersions were obtained using mechanical shear and squeeze flow rheometry combined with diffusing wave spectroscopy (DWS) and multiple particle tracking (MPT) microrheology. State diagrams were determined at inherent pH considering the clay-mineral and NaCl concentrations as well as the kinetics of structure formation and sample aging. Due to the larger mean layer diameter and greater layer-charge density of natural clay-minerals, their sol—gel transitions occurred at higher solid and NaCl concentrations than those of Laponite®. Structure formation was faster at pH < pHPZC,edge than at pH > pHPZC,edge (point of zero charge at the edge). The long-term aging of natural clay-mineral samples was less pronounced in the glass state than in the gel state, in contrast to the findings for Laponite®. The storage modulus, G’, of clay-mineral dispersions in arrested states remained essentially constant in a wide frequency range (up to 100 rad/s), as expected. The corresponding plateau value of G’ depends on the number of particle contacts per volume and, hence, increased with decreasing particle size at a given concentration. The dissipation mechanisms determining the high-frequency loss modulus, G", however, are independent of particle size and, accordingly, the high-frequency crossover of G’ and G" shifted to higher values when the particle size decreased. The MPT data revealed structural refinement on the submicrometer length scale during the aging of weak hectorite gels, which was similar to the results for Laponite®. No refinement, however, occurred for montmorillonite in the glass or strong gel state.
Quantitative Mineralogy of Clay-Rich Siliciclastic Landslide Terrain of the Sorrento Peninsula, Italy, Using a Combined XRPD And XRF Approach
- M. Cesarano, D.L. Bish, P. Cappelletti, F. Cavalcante, C. Belviso, S. Fiore
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 353-369
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Quantitative mineralogical analysis of clay-bearing rocks is often a non-trivial problem because clay minerals are characterized by complex structures and are often affected by structural disorder, layer-stacking disorder, and interstratification. In the present study, internal-standard Rietveld X-ray powder diffraction (XRPD) analyses were combined with X-ray fluorescence (XRF) chemical analyses for the mineralogical characterization and quantitative analysis of heterogeneous clay-rich sedimentary rocks that are involved in a slow-moving landslide in the Termini-Nerano area, Sorrento Peninsula (Italy), in order to investigate the relationship between the mineralogy of these rocks and landslides. Slow-moving landslides are usually considered to be associated with the more weathered and surficial parts of structurally complex slopes, and mineralogical analysis can help to clarify the degree of weathering of siliciclastic rocks. XRPD quantitative analyses were conducted by combining the Rietveld and internal standard methods in order to calculate the amounts of poorly ordered phyllosilicate clays (considered amorphous phases in Rietveld refinements) by difference from 100%. The vbAffina program was used to refine the amounts of mineral phases determined with XRPD using the element compositions determined by XRF analysis. XRPD analyses indicated that the samples mainly contain several different clay minerals, quartz, mica, and feldspars. Analysis of the clay fraction identified kaolinite, chlorite, and interstratified illite-smectite (I-S) and chlorite-smectite (C-S). The mineralogy of the materials involved in the landslide in comparison with the mineralogy of the “undisturbed” rocks showed that the landslide is located in the weathered realm that overlies an arkosic bedrock. The interstratified I-S and C-S occurred at landslide activity locations and confirmed that areas more susceptible to sliding contained the most weathered parts of the rocks and perhaps represent areas of past and currently active fluid flow.
Adsorption Of Cs+ and IO3− Ions by Pseudoboehmite Before and After the Decomposition of Citrate Adsorbed on Its Surface
- Motoharu Kawano, Eri Yamada
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 370-378
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Citrate is distributed widely in the Earth’s surface environments as a biological product released by microbes and plants. Citrate is also often used as a chelating agent for the selective dissolution of iron coatings and free iron oxides in soils. Adsorption experiments of Cs+ and IO3− before and after the complexation of citrate with the pseudoboehmite surface were conducted to evaluate the effects of citrate on the adsorption of these ions on the surface of pseudoboehmite. Additional adsorption experiments of Cs+ and IO3− after the decomposition of citrate adsorbed on the pseudoboehmite surface were also performed to confirm the recovery of the original surface properties. Citrate decomposition was carried out by means of 10% H2O2 treatments at 75°C and pH 5, 7, and 9. The results indicated that citrate complexation decreased remarkably the adsorption of both Cs+ and IO3− in the pH range 3–10, which was due to a decrease in the number of active charged sites available for adsorption of these ions. Decomposition of citrate adsorbed on the pseudoboehmite surface was found to be complete after three rounds of treatment with 10% H2O2 at 75°C and pH > 7. After the decomposition of citrate adsorbed on the pseudoboehmite surface, the adsorption of both Cs+ and IO3− was restored completely to the initial amounts before citrate complexation, and the inhibition effect of citrate on the adsorption of these ions disappeared under all pH conditions.
Polytype Identification in Trioctahedral 1:1 Layer Silicates Using Electron Diffraction with Application to a Chronstedtite That was Synthesized Using Metallic Iron-Clay Interactions
- Jiří Hybler, Mariana Klementová, Markéta Jarošová, Isabella Pignatelli, Régine Mosser-Ruck, Slavomil Ďurovič
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 379-402
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The present study presents a generalized procedure to accurately identify trioctahedral 1:1 layer silicates. The reciprocal space (RS) sections were obtained by the precession method by “unwarping” frames that were recorded using diffractometers with area detectors or from electron diffraction tomography (EDT) patterns. Distributions of subfamily reflections along the reciprocal lattice rows [21̄l]* / [11l]* / [1̄2l]* in (2hh̄lhex)* / (hhlhex)* / (h̄2hlhex)* RS planes were used to determine OD (Ordered — Disordered) subfamilies (Bailey’s groups A, B, C, D). The distributions along the [10l]* / [01l]* / [1̄1l]* rows in the (h0lhex)* / (0klhex)* / (h̄hlhex) RS planes allow determination of the polytypes. The use of traditional identification diagrams for the determination of OD subfamilies and polytypes was generalized in order to identify monoclinic and orthorhombic MDO (Maximum Degree of Order) polytypes. In these polytypes, the distribution of characteristic reflections along rows is different in RS sections that are perpendicular and diagonal to the symmetry plane of the polytype. The identification diagram of non-MDO polytype 6T2 is also presented. The method was applied to the identification of single crystals of cronstedtite that were synthesized during interactions of Fe metal with a natural claystone during experiments over a temperature range of 90-60°C. Conical and pyramidal crystals with a maximum size of a few micrometers were studied using electron diffraction tomography (EDT). The following polytypes were identified: 1M, 2M1, an apparently ninetuple polytype that was interpreted as triclinic 3A (group A), 1T (group C), and disordered crystals of group D. The 1M polytype was the most abundant. Some 1M crystals were twinned by reticular merohedry with a 120° rotation along the chex axis as the twin operation. The 2M1 occurred as isolated crystals as well as in mixed crystals. Intergrown 1T and 1M polytypes of the C and A group, respectively, were identified in one mixed crystal. The possible stacking sequence and the 3A polytype identification diagram was presented and discussed. Example RS sections of all polytypes were identified and demonstrated.