Injection of CaCl2 and Na2SiO3 solutions into clay suspensions during electroosmosis often improves the cohesive strength of clays near the anode and cathode, whereas the cohesive strength of clays between the electrodes remains weak. Although the main improvement mechanism for the cohesive strength of clays near the cathode was demonstrated to be a pozzolanic reaction (formation of calcium silicate hydrate cement), the mechanism of improved cohesive strength near the anode is still not understood. The objective of the present study was to investigate the mechanism for the improvement of cohesive strength near the anode and, thus, make it possible to determine a way to enhance the range in improvement using kaolinite as the test clay. The test was performed by first injecting CaCl2 solution during electroosmosis until the optimum volume of CaCl2 was attained. This was followed by treatment with Na2SiO3 solution for different lengths of time. The results indicate that the anode region after treatment was acidic (pH = 4) because the electrolysis of water causes acidification near the anode. As Na2SiO3 solution was injected through the anode, the mechanism of cohesive strength improvement of the treated clay near the anode was attributed to the silicic acid polymerization effect provided by the Na2SiO3 solution. The silicic acid may link the clay particles together to form a gel network in a low pH environment. The clay gel network structure developed rigidity as the water content was reduced. In addition, as the volume of injected Na2SiO3 solution was increased, the cohesive strength near the anode also increased.

Dark Fe oxides and sulfides are major discoloring impurities in mined commercial white kaolin clay. In order to evaluate the potential influence of Fe-cycle bacteria on Fe cycling during post-depositional clay-weathering alteration, Fe(III)-reducing and/or Fe(II)-oxidizing microorganisms were examined in open-pit, subsurface mine samples from kaolin lenses and smectite formations collected from sites in central Georgia. Samples of varying age were examined, including late Eocene smectite overburden, hard kaolin of Middle Eocene age, soft gray kaolin from the late Paleocene, and soft tan kaolin of late Cretaceous age. These clays contained 0.06–5.33% organic carbon, which included various potential organic electron donors for bacterial metabolism: formate (1.1–30.6 mmol/kg), acetate (0–40.5 mmol/kg), lactate (0–12.1 mmol/kg), pyruvate (0.4–78 mmol/kg), oxalate (0–141.7 mmol/kg), and citrate (0–1.4 mmol/kg). All clay samples studied had small concentrations of ‘bio-available’ Fe(III) (0.5 M HCl-extractable Fe, 0.5–2.8 mmol/kg) compared to total Fe (HF-extractable, 25–171.9 mmol/kg). The highest Fe(III)/[Fe(II)+Fe(III)] ratio and the lowest organic carbon content were in kaolin samples in which Fe(III) reduction was determined to be the dominant terminal electron accepting process by hydrogen analysis. All clay samples showed greater numbers of Fe(II)-oxidizing bacteria (22–22,000 cells/g) than Fe(III)-reducing bacteria (3–410 cells/g) as determined by MPN analysis. The Fe(III)-reducing activity in clays could be stimulated with the addition of 1 mM of the Fe(III) chelator, nitrilotriacetic acid. The addition of nitrate stimulated anaerobic Fe(II) oxidation. These results suggest that anaerobic bacteria involved in both oxidation and reduction of Fe exist in these subsurface clay formations, and might have had an influence on post-depositional weathering reactions.

The equivalent diffuse double layer (DDL) thickness in clay-electrolyte systems is a very useful parameter for analyzing the engineering behavior of clays under different environmental conditions. The equivalent DDL thickness is generally assumed to be equal to the characteristic (Debye) length. The present work examined critically the applicability of characteristic length to define equivalent DDL thickness under various clay-surface and pore-fluid conditions. A critical analysis is presented of the changes in the equivalent DDL thickness and characteristic length under the influence of different clay-surface and electrolyte properties. The equivalent DDL thickness was found to be smaller than the characteristic length for a wide range of surface and pore-fluid parameters normally encountered in engineering practice. An accurate and simple power relationship was developed to predict the equivalent DDL thickness from the characteristic length, which is applicable to a wide range of clay-electrolyte systems.

Bentonite from the ‘Bogovina’ coal mine in Serbia, was characterized. The influence of acid treatment on its composition, as well as mathematical descriptions of this influence are reported. The purpose of this work was to correlate the concentration of the acid used for the treatment with the resulting bentonite composition. X-ray diffraction (XRD), infrared spectroscopy and quantitative chemical analysis were employed to define the changes caused by acid treatment.

The contents of all the cations, except Si, decreased exponentially with increasing concentration of the HCl used for the treatment of the bentonite. This approach was tested on previously published data and was shown to be valid.

The basal reflections of smectite decreased gradually and eventually disappeared after intense treatment, while the other reflections remained in the XRD patterns of all the samples, but decreased slightly with increasing acid strength. In addition, the amount of X-ray amorphous matter formed increased rapidly with increasing acid concentration up to 4.5 M. With further increase in the acid strength, the amount of X-ray amorphous matter remained virtually constant.

The Serinhisar-Acıpayam basin of western Anatolia hosts a Neogene alkaline lake which formed in some graben and semi-graben depression zones as a result of N–S tension. The basin is filled with fluvial and lacustrine sediments dominated by clayey materials. The filling of the basin with fine sediments and associated water level changes caused the development of swampy and/or semi-swampy, alkaline-lake environments where sepiolite, palygorskite, saponite and dolomitic sepiolite or palygorskite precipitated periodically in the basin. Sepiolite is predominant in the Kuyucak section and is intercalated with saponite-dominated levels, whereas saponite accompanied palygorskite at Kocapınar where basaltic volcanism occurred. The contacts between sepiolite-palygorskite and saponite levels are more or less sharp, reflecting rapid changes in the physicochemical conditions of the depositional environment. Micromorphological images reveal that both sepiolite and palygorskite grew as interwoven fibers or fiber bundles and masses where dolomite was absent, indicating direct precipitation from solution, whereas fibrous networks grew authigenically on and out of dolomite in dolomitic sepiolite and dolomitic palygorskite. Saponite is either green or reddish brown due to its organic material-rich content and derivation from products of basaltic volcanism. Synsedimentary basaltic volcanism was the main source of Fe and Al, whereas Si and Mg were derived from surrounding ultrabasic and detrital units and partly from the volcanism. It can be concluded that sepiolite, palygorskite and saponite formed either by direct precipitation from alkaline lake water or authigenically from interstitial pore-water between dolomite rhombs as controlled by concentration of Si, Mg, Al and Fe, rather than by mutual transformation.

Illite-smectite (I-S) minerals isolated from Upper Jurassic oil-source rock shales from Denmark and the North Sea have been investigated by X-ray diffraction, thermal analysis, infrared, Mössbauer, and solid-state nuclear magnetic resonance spectroscopies and chemical analysis. Detailed structures have been determined in order to reveal the diagenetic transformation mechanism in these shales. Generally, in oil-source rocks of sedimentary basins, oil generation takes place simultaneously with the diagenetic transformation of I-S. We demonstrate a link between the two reactions: NH3 released from kerogen during maximum oil generation is fixed as NH4+ in the NH4-bearing mica or tobelite layers formed from smectite or vermiculite layers in I-S, in a diagenetic interval which we name the ‘tobelitization window’. Due to this solid-state transformation, mixed-layer structures have been formed consisting of interstratified illite, tobelite, smectite and vermiculite layers (I-T-S-V) and having maximum ordering of illite + tobelite and smectite layers for R = 1. The tobelitization of smectite in I-S is probably typical for all oil-source rock shales.

Because of their isolating capacity, smectite-rich clays have been proposed as buffer and backfill materials in high-level radioactive waste repositories. These repositories have to guarantee long-term safety for ~1 million years. Thermodynamics and kinetics of possible alteration processes of bentonite determine its long-term performance as a barrier material. Smectites in 25 different clays and bentonites were investigated in order to identify possible differences in their rates of alteration. These samples were saturated for 30 days in 1 M NaCl solution and deionized water, and then overhead rotated at speeds of 20 rpm and 60 rpm. Depending on the octahedral and interlayer composition, each of the smectites studied had specific rate of alteration, a so-called specific dissolution potential of smectite. The bentonites were classed as ‘slow-reacting bentonite’, ‘moderate-reacting bentonite’, or ‘fast-reacting bentonite’ corresponding to a relatively low (ΔP specific dissolution potential — <-5%), moderate (-5% < ΔP < -20%), or high specific dissolution potential (ΔP > -20%), respectively. The larger the amount of octahedral Fe and Mg compared to octahedral Al, the greater the specific dissolution potential. The present study found that the interlayer composition has a discernible impact on the rate of alteration. In experiments with rotation speeds of 60 rpm and a 1 M NaCl solution, Na+ was found to be the stabilizing cation in the interlayers of all the smectites. The Na-stabilizing mechanism was identified in only some of the smectites (type A) in experiments with 20 rpm (1 M NaCl solution). A second stabilization mechanism (by interlayer cations; Ca and Mg) was identified for other smectites (type B). Each bentonite has a specific rate of alteration. ‘Slow-reacting bentonite’ and clay with smectite-illite interstratifications are recommended as potential clay barriers in HLW repositories. The experimental and analytical procedures described here could be applied to potential barrier materials to identify ‘slow-reacting bentonite’.

Chrysotile from Thetford Mines in Quebec, Canada was treated first with mild formic or oxalic acid at concentrations of 0.5 to 2.0 N at 200°C in Teflon-lined 12.0 mL Parr bombs. The reaction products were identified by X-ray diffraction as a poorly crystalline Fe-bearing kerolite-like 2:1 layer silicate (which will be described as a kerolitic precipitate or a kerolitic mesophase in this report). Electron microscopic examination showed a thin foily morphology for this kerolitic mesophase that may have formed by the following reaction:(1)

$\mathop {{\rm{M}}{{\rm{g}}_{\rm{6}}}{\rm{S}}{{\rm{i}}_{\rm{4}}}{{\rm{O}}_{{\rm{10}}}}{{\left( {{\rm{OH}}} \right)}_{{8_{\left( {\rm{s}} \right)}}}}}\limits_{{\rm{chrysotile}}} + 6.02{{\rm{H}}^{\rm{ + }}}_{\left( {{\rm{aq}}} \right)} + 0.54{\rm{F}}{{\rm{e}}^{{\rm{2 + }}}}_{\left( {{\rm{aq}}} \right)} \to \mathop {\left( {{\rm{M}}{{\rm{g}}_{{\rm{2}}{\rm{.46}}}}{\rm{Fe}}_{{\rm{0}}{\rm{.54}}}^{{\rm{2 + }}}} \right){\rm{S}}{{\rm{i}}_{\rm{4}}}{{\rm{O}}_{{\rm{10}}}}{{\left( {{\rm{OH}}} \right)}_{\rm{2}}} \cdot n}\limits_{{\rm{kerolitic}}\;{\rm{mesophase}}} {{\rm{H}}_{\rm{2}}}{{\rm{O}}_{\left( {\rm{s}} \right)}} + {\rm{3}}{\rm{.55M}}{{\rm{g}}^{{\rm{2 + }}}}_{\left( {{\rm{aq}}} \right)}$

The magnetite impurity in the initial chrysotile asbestos served as the source of Fe in the above reactions. Subsequently, this kerolitic precipitate was reacted with 0.2 N NaOH for 48–96 h at 200°C and a highly crystalline smectite was formed with the same foily morphology as the kerolitic precipitate. X-ray spectral analyses of the kerolitic mesophase and smectite suggest the following reaction to have taken place:(2)

$\eqalign{ & \mathop {\left( {{\rm{M}}{{\rm{g}}_{{\rm{2}}{\rm{.46}}}}{\rm{Fe}}_{{\rm{0}}{\rm{.54}}}^{{\rm{2 + }}}} \right){\rm{S}}{{\rm{i}}_{\rm{4}}}{{\rm{O}}_{{\rm{10}}}}{{\left( {{\rm{OH}}} \right)}_{\rm{2}}}}\limits_{{\rm{kerolitic}}\;{\rm{mesophase}}} \cdot n{{\rm{H}}_{\rm{2}}}{{\rm{O}}_{\left( {\rm{s}} \right)}} + {\rm{0}}{\rm{.53M}}{{\rm{g}}^{{\rm{2 + }}}}_{\left( {{\rm{aq}}} \right)} + 0.54{\rm{NaO}}{{\rm{H}}_{\left( {{\rm{aq}}} \right)}} + 0.01{\rm{F}}{{\rm{e}}^{{\rm{3 + }}}}_{\left( {{\rm{aq}}} \right)} \to \cr & \;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\;\mathop {\;\;{\rm{N}}{{\rm{a}}_{0.54}}\left( {{\rm{M}}{{\rm{g}}_{{\rm{2}}{\rm{.99}}}}{\rm{Fe}}_{{\rm{0}}{\rm{.01}}}^{{\rm{2 + }}}} \right)\left( {{\rm{S}}{{\rm{i}}_{{\rm{3}}{\rm{.46}}}}{\rm{Fe}}_{{\rm{0}}{\rm{.54}}}^{{\rm{3 + }}}} \right){{\rm{O}}_{10}}{{\left( {{\rm{OH}}} \right)}_{{\rm{2}}\;\left( {\rm{s}} \right)}}}\limits_{{\rm{saponite}}} + 0.54{\rm{S}}{{\rm{i}}^{{\rm{4 + }}}}_{\left( {{\rm{aq}}} \right)} \cr} $

The reaction products, a kerolitic mesophase and smectite, possess a non-fibrous habit in contrast to the fibrous (asbestiform) morphology of chrysotile.

The intercalation of europium ions (Eu3+) into the interlayer space of a layered silicate, magadiite, was conducted by ion-exchange reactions between magadiite and europium(III) chloride. X-ray diffraction and elemental analysis results indicated that Eu3+ cations were intercalated into the interlayer space of magadiite. The ion exchange between Eu3+ and Na+ occurred preferentially so that the adsorbed Eu3+ amounts were controlled quantitatively. Thermal transformation of the original layered structure was suppressed by the intercalation of Eu3+. The resulting intercalation compounds exhibited photoluminescence arising from the intercalated Eu3+. The luminescence intensity varied in accordance with the amount of Eu3+ absorbed, suggesting that the self-quenching occurred at higher loading levels. The luminescence intensity was also changed by the heat treatment, corresponding to the change in the surroundings of the Eu3+ adsorbed, induced by the removal of the adsorbed water molecules and the hydroxyl groups of the silicate.

Minerals such as quartz, present widely in various volcanic ashes, remain unaltered throughout the low-temperature hydrothermal process currently used in industry to obtain zeolites, causing an incomplete hydrothermal transformation of the starting solid. This study presents a novel and cost-effective procedure which improves the reactivity of ash toward the generation of zeolite by increasing the availability of silica and alumina components. This method leads to a final product with a large zeolite content. The transformation consisted of an ash-activation step followed by hydrothermal zeolitization. The influence of the structural, chemical, and morphological characteristics of the volcanic ash as well as the effect of the activation procedure on the ash reactivity were studied. A collected sample (VA) and an amorphous fraction obtained after VA sieving (VA40, retained on #40 mesh) were used for zeolite production. These solids were alkaline-treated separately, aged, and reacted under controlled conditions of temperature at autogenous pressure. Throughout the process, the solid phases were characterized by X-ray diffraction, energy dispersive X-ray microanalysis, scanning electron microscopy, Fourier-transform infrared spectroscopy, and N2adsorption-desorption porosimetry measurements. After activation and alkaline aging, the presence of quartz and plagioclase minerals in the natural ash seemed to improve the growth of NaAlSiO4 polymorphs, which in turn were transformed easily to zeolite structures. Even under adequate pretreatment and suitable synthesis conditions, the coarse non-crystalline fraction led to low conversion, while the highest conversions to zeolites A and X were obtained from the natural ash. The outcomes of the present study could be used to improve the conversion levels of other non-conventional aluminosiliceous minerals into zeolites.

Many important properties of clay minerals are defined by the species of charge-balancing cation. Phenomena such as clay swelling and cation exchange depend on the cation species present, and understanding how the cations bind with the mineral surface at a fundamental level is important. In the present study the binding affinities of several different charge-balancing cations with the basal surface of the smectite mineral, montmorillonite, have been calculated using molecular dynamics in conjunction with the well-tempered metadynamics algorithm. The results follow a Hofmeister series of preferred ion adsorption to the smectite basal surfaces of the form:

K+ > Na+ > Ca2+ > Cs+ > Ba2+

The results also revealed the energetically favorable position of the ions above the clay basal surfaces. Key features of the free-energy profiles are illustrated by Boltzmann population inversions and analyses of the water structures surrounding the ion and clay surface. The results show that weakly hydrated cations (K+ and Cs+) preferentially form inner-sphere surface complexes (ISSC) above the ditrigonal siloxane cavities of the clay, while the more strongly hydrated cations (Na+) are able to form ISSCs above the basal O atoms of the clay surface. The strongly hydrated cations (Na+, Ca2+, and Ba2+), however, preferentially form outer-sphere surface complexes. The results provide insight into the adsorption mechanisms of several ionic species on montmorillonite and are relevant to many phenomena thought to be affected by cation exchange, such as nuclear waste disposal, herbicide/pesticide-soil interactions, and enhanced oil recovery.

Sub-surface clay samples are difficult to characterize using conventional methods so non-invasive Nuclear Magnetic Resonance (NMR) techniques were used to evaluate in a preserved state the pore structure, porosity, water mobility, and affinity of various clay systems. Within the CLAYWAT project launched by the NEA Clay Club, some of the most advanced NMR techniques were applied to samples from 11 clay-rich sedimentary formations (Boom Clay, Yper Clay (both Belgium); Callovo-Oxfordian shale, Upper Toarcian (both France); Opalinus Clay from two sites (Switzerland); Queenston Fm., Georgian Bay Fm., Blue Mountain Fm. (all Canada); Boda Clay (Hungary); and Wakkanai Fm. and Koetoi Fm. (Japan)). The degree of induration within this suite of samples varies substantially, resulting in a wide porosity range of 0.02–0.6. The key finding is the determination of pore-size distribution by NMR cryoporometry in the range of 2 nm–1 μm with the native fluid present in the pore space for most samples. The water volume in pore sizes of <2 nm could also be measured, thus providing a full description of the porosity system. A specific preparation by sample milling was applied to the preserved original cores minimizing disturbances to the samples in terms of water loss. The water content measured by NMR relaxation was comparable to values obtained by drying at 105°C. In general, the narrow T2 distributions indicate that water was diffusing throughout the pore network during the magnetization lifetime, implying that T2 distributions cannot be considered as proxies for the pore-size distributions. For the set of samples considered, the T1/T2 varied between 1.7 and 4.6, implying variable surface affinity. Finally, for most samples, a pore-shape factor of ~2.4, intermediate between a sheet (1) and a cylinder (4), was deduced.

Two soil sequences in northern Italy (Val di Fiemme and Val Genova) along an elevational gradient ranging from moderate (950 m a.s.l.) to high alpine (2440 m a.s.l.) climate zones were investigated with respect to element losses (Ca, Mg, K, Na, Fe, Al, Si, Mn) and development of clay minerals. Soils formed on paleo-rhyolitic parent material in Val di Fiemme and on tonalitic-granodioritic morainic material in Val Genova. All the soils have a similar age (∼12,000 y) and have been classified as Podzols. The soils are very acid and the pH values tend to increase with decreasing altitude. Podzolization processes were most intense in the range of the subalpine forest up to the timberline (1400–1900 m above sea-level (a.s.l.)). Element leaching was greatest in this range and weathering rates decrease with both higher and lower altitudes. Due to the different lithologies and precipitations between the two valleys, the total amount of chemical weathering was slightly different, although the same trends with altitude could be observed. Imogolite-type materials (ITM) are generally of minor importance. Greater concentrations of ITM were observed in the Bhs or Bs horizons of the Episkeleti-Entic Podzols at the lower altitudes. Iron eluviation was similar in all Podzols while larger amounts of eluviated Al were detected in Val Genova. The pattern of smectite distribution along the climosequences had similarities to the trend of cation losses. The largest amount of low-charge expandable minerals seems to exist in the range of the subalpine forest up to the timberline. The development of clay minerals with a smaller layer charge was more advanced in Podzols on rhyolitic material where smectite could be detected in the Bhs and Bs horizon. Parent material influenced chemical weathering in the soils along the two climosequences and essentially determined the degree of weathering and the formation of clay minerals.

The present study compares the water-vapor adsorption capacity of bentonites (natural cation population) with the Enslin-Neff method. Water-vapor adsorption at 50% r.h. (relative humidity) or 70% r.h. is known to depend heavily on the amount of permanent charge and on the type of exchangeable cation. At ~80% r.h. Na+- and Ca2+/Mg2+-dominated bentonites take up equal amounts of water. Comparing the water-uptake capacity at 80% r.h. with the cation exchange capacity (CEC) revealed a close correlation between these two variables. Appreciable scatter apparent from this plot, however, suggests that additional factors influence the water-uptake capacity.Water adsorption at external surfaces was considered to be one of these factors and was, in fact, implicated by N2-adsorption data. The ratio of external/internal water ranged from 0 to 1, which suggests that water-adsorption values cannot be applied in the calculation of the internal surface area without correction for external water.

The Enslin-Neff water-uptake capacity, on the other hand, is unaffected by microstructural features (e.g. specific surface area and porosity). The amount of exchangeable Na+ is themost important factor. However, the relationship between the Na+ content and the Enslin value is not linear but may be explained by percolation theory.

The Şile Region contains discontinuous, cyclic, thin coal beds and industrial clay deposits that were accumulated in lacustrine basins which received extensive volcanoclastic sediments due to transport of highly weathered calc-alkaline volcanic rocks. The Sülüklü area has the largest kaolin deposit in this region. Cyclic kaolinization depended on the degree of leaching of Si and alkalis in cyclic swamp environments and, therefore, kaolinite contents vary in each discontinuous lens-shaped clay bed and underclay within the basin. The kaolins comprise disordered kaolinite, illite, smectite, gibbsite, quartz, pyrite, anatase, K-feldspar and goethite. Depth-related changes in the distribution of clay minerals, associated with coal beds, are indicative of organic acid-mineral reactions. Kaolinite crystallization initiated at the edges of sericitic mica sheets in the form of composite kaolinite stacks. The small size (<1 µm), morphology and poor crystallinity of kaolinite crystals suggest that kaolinization post dated transportation. Primary or secondary origins of particles can be determined from the stacking sequences of kaolinite particles using high-resolution transmission electron microscopy images. Kaolinite stacks always contain a small amount of illite, but smectite is only present in the middle and upper levels. Gibbsite is a main constituent of refractory bauxitic clays locally found as discontinuous lenses and exploited from the lower level of the basin.

Genesis of kaolin deposits took place in two stages: first, there was in situ weathering of the oldest andesitic agglomerates, tuffs and ashes at the base of the lacustrine basin coupled with discharge of shallow thermal waters which were initiated by local hydrothermal alteration; second, surface weathering enhanced transportation of altered rocks from the surrounding hills into the lacustrine basin. Kaolinization took place in cyclic swamp environments, as indicated by the presence of cyclic thin- to thick-bedded coals that provided necessary humic and fulvic acids for the post-depositional alteration of altered volcanic rocks to kaolin in dysaerobic, relatively low-pH conditions in saturated groundwater zones.

Natural mineral materials such as tabular and spheroidal halloysites have recently been suggested as candidates for intercalating metal ions or organic molecules. Their potential use as nanoadsorbents is related to their porous structure and water content. Although the two morphologies can coexist in natural deposits, spheroidal halloysites remain poorly characterized whereas much literature exists on tubular halloysites. The present study investigates the native morphology, internal porous structure, and behavior upon dehydration of spheroidal halloysite from Opotiki (New Zealand). This mineral was characterized in its natural hydrated state using a transmission electron microscope equipped with an environmental cell (EC-TEM). The sample was placed in a sealed block in which water vapor-saturated air circulated at a pressure of 30 Torr. The observed particles consisted of almost complete spheroids displaying polyhedral external surfaces. 1:1 layers stack concentrically as a pore-free, onion-like structure. The dynamic processes of dehydration created by slow depressurization of the cell resulted in a decrease in the layer-to-layer distance (d001) from ~10 Å to ~7 Å due to the loss of interlayer water molecules. Irreversible formation of spurious ‘internal pores’ was recorded during this process. These pores were not indigenous to the hydrated 10 Å halloysite and resulted from the collapse of the native layers. They cannot account for the physical chemical properties of spheroidal halloysite. Spheroidal halloysites would have a lower propensity for intercalating ions or molecules than tubular halloysites. Isolated facets were also observed in high-resolution-TEM and displayed a pseudo-hexagonal morphology. The three-dimensional microstructure of the spheroid appeared bent along the three pseudo equivalent yi directions of the kaolinite-like single layers. An analogy with polyhedral serpentine has allowed the proposal of a formation process of hydrated spheroidal halloysite triggered by enrichment in divalent ions in the growth system.