The dehydration reaction of kerolite was investigated using high-pressure differential thermal analysis at pressures as high as 600 bars. The peak associated with the dehydration is broad, suggesting the presence of a series of overlapping reactions ranging from the release of adsorbed water to interlayer water. The peak temperature is 136°C at 1.8 bars and increases to 516°C at 586 bars. The primary reaction represents loss of adsorbed water having a bond energy of 1.5 ± 1 kJ/mole. A small amount of water may be present as interlayer water and has a bond energy of 7.5 ± 3 kJ/mole.

Mixed-layer clays composed of randomly interstratified kerolite/stevensite occur as lake and/or spring deposits of probable Pliocene and Pleistocene age in the Amargosa Desert of southern Nevada, U.S.A. The percentage of expandable layers of these clays, determined from computer-simulated X-ray diffractograms, ranges from almost 0 to about 80%. This range in expandabilities most likely results from differences in solution chemistry and/or temperature at the time of formation. An average structural formula for the purest clay (sample P-7), a clay with about 70% expandable layers, is:

$${\left[ {\left( {M{g_{2,72}}A{l_{0,07}}F{e_{0.03}}L{i_{0.09}}} \right)\left( {S{i_{3.96}}A{l_{0.04}}} \right){O_{10}}{{\left( {OH} \right)}_2}} \right]^{ - 0.21}}{\left[ {X_{0.21}^ + } \right]^{ + 0.21}}.$$

The data suggest that talc, kerolite, and stevensite form a continuous structural series based on layer charge.

Two kerolite and one garnierite samples were subjected to progressive heat treatments prior to their examination by infrared spectroscopy (IR) in the 1200-600-cm−1 and 3800-3000-cm−1 regions. The heat treatment of the garnierite (a mixture of nepouite and pimelite) selectively dehydroxylated the nepouite thus allowing an examination to be made of the OH-vibration bands due to the pimelite. Both the relative intensities of the 710-670-cm−1 doublet and of the different OH-stretching bands indicated the Ni content of this pimelite to be about 70%. The heat treatments did not modify the 1200-600-cm−1 region of the spectra of kerolites but caused a noticeable sharpening in the OH-stretching region. The relative intensities of the structural OH-stretching bands of dehydrated kerolites showed that they differ from Ni-talcs of similar composition in the distribution of Ni and Mg in the octahedral sites. These cations are randomly distributed in Ni-talc but are mainly segregated into Mg and Ni domains in kerolite. Changes in sharpness, intensity, and position of the structural OH-stretching bands of the kerolites as temperature increases and dehydration progresses are similar to those undergone by Mg- or Li-saturated trioctahedral smectites. Also thermal analysis curves of these minerals show similarities with those of Mg- and Ni-saturated smectites, and suggest that in kerolites too, the hydration water is associated with interlayer (though non-exchangeable) Ni and/or Mg cations.

Deposits of sepiolite, trioctahedral smectite (mixed-layer kerolite/stevensite), calcite, and dolomite, found in the Amargosa Flat and Ash Meadows areas of the Amargosa Desert were formed by precipitation from nonsaline solutions. This mode of origin is indicated by crystal growth patterns, by the low Al content for the deposits, and by the absence of volcanoclastic textures. Evidence for low salinity is found in the isotopic compositions for the minerals, in the lack of abundant soluble salts in the deposits, and in the crystal habits of the dolomite. In addition, calculations show that modern spring water in the area can precipitate sepiolite, dolomite, and calcite following only minor evaporative concentration and equilibration with atmospheric CO2. However, precipitation of mixed-layer kerolite/stevensite may require a more saline environment. Mineral precipitation probably occurred during a pluvial period in shallow lakes or swamps fed by spring water from Paleozoic carbonate aquifers.

The Sinya Beds of the Amboseli Basin in Tanzania and Kenya consist largely of carbonate rocks and Mg-rich clays that are intensely deformed where exposed in and near former meerschaum mines. The carbonate rocks consist of limestone and dolomite in Tanzania, but only dolomite has been identified in Kenya. Sepiolite and mixed-layered kerolite/stevensite (Ke/St) are subordinate constituents of the carbonate rocks. The carbonate rocks and overlying bedded sepiolite were deposited in a semiarid lake basin at the foot of the large volcano Kilimanjaro. Calcite and dolomite of the carbonate rocks have δ18O values 4–6‰ lower than calcite and dolomite of the late Pleistocene Amboseli Clays, suggesting that the Sinya Beds were deposited in the middle or early Pleistocene under a different climatic regime when meteoric water had lower δ18O values than at present.

Mg-rich clay minerals form veins and fill cavities in the Sinya Beds. The principal clay minerals are sepiolite and Ke/St, some of which contains substantial Al and Fe (Al-Ke/St). NEWMOD® modeling and other X-ray diffraction (XRD) data suggest that most of the Ke/St contains 25–50 percent kerolite layers, but minor amounts of kerolite-rich Ke/St are present in some samples. Illite with an inferred high content of Fe or Mg is a minor constituent of the samples with Al-Ke/St. The cavity-filling clays were chemically precipitated, as shown by field relationships and SEM study. The early-deposited clays of veins and cavities are principally Ke/St with minor sepiolite, and the latest clay is sepiolite (meerschaum), generally with minor Ke/St.

The δ18O values of cavity-filling Ke/St range from 22.5–25.6‰ and correlate with mineral composition, with the highest values associated with the highest content of stevensite and the lowest values with the highest content of kerolite. This relation suggests that high salinities favored stevensite and low salinities favored kerolite. δ18O values of sepiolite (meerschaum) fall in the middle of the range for Ke/St, suggesting that salinity was not the main control on sepiolite precipitation. High values of $a_{Si{O}_2}/a_{M{g}^{2+}}$ may have been a major factor in sepiolite precipitation.

Different mixtures of dilute ground water and saline, alkaline lake water in pore fluids may largely account for the differences in clay mineralogy of cavity-filling clays. Sepiolite is the dominant clay mineral in lacustrine sediments of the Amboseli Basin, and the cavity-filling sepiolite may reflect a high proportion of lake water. The low-Al Ke/St may have formed from fluids with a higher proportion of ground water. Detrital clay was very likely a factor in forming the Al-Ke/St, for which δ18O values suggest a saline environment.

Stevensite-like sauconite, with the general composition: ${\text{Si}}_4\left({\text{Zn}}_{3-x}{\square }_x\right){\text{O}}_{10}{\left(\text{OH}\right)}_2{R}_{2x}^{+}$\$\end{document}, where □ is a vacant site, was synthesized. The objective was to study the possible migration of some cations (Li+ and Zn2+) within such trioctahedral smectites, under heating, following the so-called ‘Hofmann-Klemen’ (HK) effect. The initial gel was divided into five aliquots and placed in teflon-coated hydrothermal reactors with distilled water, and these were hydrothermally treated at 80, 100, 120, 150, and 200°C, respectively, over 30 days. X-ray diffraction (XRD) analysis confirmed that the samples synthesized were smectites. The number of vacant sites (x) per half unit cell (O10(OH)2) ranged from nearly 0 to 0.23 but no simple relationship was established between x and the temperature of synthesis. The samples were Li+- and Zn2+-saturated, and heated overnight at 300°C (HK treatment). Cation exchange capacity measurements were made by Fourier transform infrared spectroscopy (FTIR) on ${\text{NH}}_4^{+}$\$\end{document}-saturated samples. After LiHK treatment, the structural formula of samples could be expressed as: ${\text{Si}}_4{\text{Zn}}_{\left(3-x\right)}{\text{Li}}_x{\text{O}}_{10}{\left(\text{OH}\right)}_2{\text{NH}}_{4x}^{+}$\$\end{document}, while after ZnHK treatment, it could be expressed as: Si4Zn3O10(OH)2. Analysis by XRD and FTIR showed that the samples moved from a Zn-stevensite-like structure to Zn-talc-like structure after treatment with ZnHK. These results are interpreted asevidence that Zn2+ (and Li+) migrated into the previously vacant sites under HK treatment.

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.

Understanding clay-mineral assemblages forming in saline lakes aids in reconstructing paleoenvironments on Earth and other terrestrial planets; this is because authigenic phyllosilicates are sensitive to the prevailing geochemical conditions present during formation. In most geochemical models, evaporative concentration favors sepiolite with increasing silica and Mg2+ concentrations without considering the role of the biogenic removal of silica from solution by diatoms. In the present study, phyllosilicates occurring in the mudflats of Bolivian salars were investigated to aid in understanding the geochemical factors that control mineral assemblages forming in (SO42–)- and (Cl–)-rich environments in relation to dissolved silica. From transects across the mudflats, the physical, chemical, and mineralogical characteristics of the bulk sediment and the <2 μm fraction of each sedimentary layer were analyzed. From these analyses, three types of sediments were identified: (1) regolith sediments dominated by Al-dioctahedral smectite, illite, and chlorite; (2) detritus-rich mudflat sediments with Mg-trioctahedral smectite and Al-dioctahedral smectite along with illite and chlorite; and (3) authigenic mudflat sediments dominated by poorly formed Mg-trioctahedral smectite, kerolite, and biogenic silica. The absence of sepiolite-palygorskite in the salars is the result of excessively high Mg:Si ratios within the waters. In the surface water Mg becomes enriched relative to Si as diatoms remove dissolved Si from solution through biologically mediated uptake. The geochemical conditions present within the salars that act to preserve the diatom frustules and prevent their dissolution include: neutral–slightly alkaline pH solutions, cold temperatures, shallow water, and high salinity. Under these conditions the formation of sepiolite is restricted by the small amount of dissolved silica, despite the silica-rich environment. The formation of Mg-smectite and kerolite is favored under these conditions.

Most of the world's sepiolite-palyg orskite precipitates in lacustrine and perimarine environments. Although these minerals can transform from precursor minerals, the most common formation mechanism involves crystallization from solution. In this study, equilibrium activity diagrams are calculated for sepiolite-palygorskite in the seven component system MgO-CaO-Al2O3-SiO2-H2O-CO2-HCl, employing available thermodynamic data for related minerals, aqueous species and water. Stability fields are illustrated graphically on plots of log $[a_{{\text{Mg}}^{2+}}\text{/}{(a_{{\text{H}}^{+}})}^2]$vs. log $[a_{{\text{H}}_{\text{4}}{\text{SiO}}_{\text{4}}}{}^{\text{o}}]$, using the activities for log $[a_{{\text{Al}}^{3+}}\text{/}{(a_{{\text{H}}^{+}})}^3]$ defined by an arbitrarily chosen value and the approximate saturation limits of pyrophyllite + amorphous silica, kaolinite + amorphous silica, kaolinite + pyrophyllite, pyrophyllite + quartz and gibbsite. The formation of sepiolite-palygorskite from solution is more favored in the presence of amorphous silica than quartz. Lower aqueous aluminum activities favor the non-aluminum phases sepiolite and kerolite relative to the aluminum-containing phases palygorskite and saponite. The stability ranges of worldwide associations of magnesite and dolomite with sepiolite and palygorskite are also illustrated as a function of aluminum activity.

The occurrence of kerolite in association with various secondary Ca-Mg carbonate mineral deposits (speleothems) was identified in basaltic sea caves on the island of Kauai, Hawaii. Kerolite is the dominant clay mineral in the deposits. X-ray diffraction (XRD) peaks of the kerolite are characteristically broadened indicating its extremely poor crystallinity. Few changes were observed in the XRD patterns of this kerolite when it was subjected to various humidity, temperature and ethylene-glycol treatments. The crystals appear as flaky masses with irregular or jagged edges in scanning (SEM) and transmission electron microscopy (TEM). Electron probe and energy dispersive X-ray (EDX) microanalysis show that the clay material is dominated by Mg-Si-O, with minor amounts of Al and Ca in some samples. The chemical composition, thermal analysis and TEM observations suggest that smaller amounts of an amorphous serpentine-like phase are mixed with the kerolite. Kerolite is often the only mineral associated with poorly mineralized, actively-growing microbial mats in these caves and it is common in completely lithified microbial mats. The latter commonly have microstromatolitic structures with kerolite as a dominant phase. These features suggest that kerolite formation is at least in part a result of microbial activity. The abundant extracellular polymers of the mat-forming bacteria bind and concentrate ions (Mg2+, silica) from solution and serve as nucleation sites for kerolite precipitation. Conditions within the mats also probably lead to formation of Mg-Si-gels, amorphous Mg-silicate precursors and ultimately kerolite. Evaporation of the cave solutions may also contribute to kerolite formation.

Mg-silicate minerals (e.g., stevensite, kerolite, talc, sepiolite) play an important role in the construction of facies models in lacustrine and peri-marine environments because they are sensitive to changes in solution chemistry. However, the response of Mg-silicate mineralogy to changing aqueous chemistry is only broadly understood because the mechanisms underpinning the coprecipitation of Mg2+ and SiO2(aq) from surface water, and subsequent Mg-silicate crystallization, are unclear. Here we describe the results of experiments designed to systematically examine the effects of pH, Mg/Si and salinity of the parent solution on the nature of initially precipitated products. Structural interrogation of the products with X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR) and thermal analysis (TGA/DTA) allow comparison of synthetic products with naturally occurring crystalline counterparts. In general, Mg2+ and SiO2(aq) co-precipitation and nucleation of Mg-silicate layer structures first involves the rapid formation of 2:1 layers with trioctahedral occupancy and a mean coherent X-ray scattering domain between 1–2 unit cells with respect to the c axis. Well defined but diffuse hk reflections indicate two-dimensional growth, turbostratic stacking and highly variable interlayer hydration. Diffuse reflectance FTIR shows numerous structural similarities with stevensite, kerolite and sepiolite. However, TGA/DTA analysis indicates the presence of variable kerolite/stevensite interstratification not readily detectable through XRD analyses, as well as a significant degree of surface and interlayer hydration (e.g. 15–20 wt.%).

We observe a number of clear trends in the products with respect to solution chemistry. For example, at low salinity, kerolite-like products dominate at high Mg/Si and high pH, whereas sepiolite-like products are formed at lower pH and lower Mg/Si. At high salinity and high Mg/Si, stevensite-like products are favoured at high pH and kerolite-like products dominate at lower pH, whereas a decrease in Mg/Si of the solution leads to sepiolite-like products at low pH and only stevensite-like products at high pH. Higher pH leads to an increase in octahedral vacancies which favour stevensite-like products; this may result from a higher rate of two-dimensional tetrahedral sheet expansion relative to the octahedral sheet, as inferred from studies of silica oligomerization and brucite growth kinetics.

Together, our results indicate that the neoformation of Mg-rich silicates from solution may often begin with the rapid nucleation of hydrated 2:1 layers. Subsequent dehydration leads to progressive layer stacking order and could occur in response to wetting/drying cycles, prolonged exposure to high salinity solutions, or burial and heating. The surface and interlayer water associated with these products is undoubtedly an important source of diagenetic water in Mg-silicate-bearing successions, and the chemistry of this water upon later diagenesis should be a focus of future investigation.

An Early Pliocene sedimentary succession in the Yenidoğan area, Sivrihisar, Turkey, consists of sepiolite, stevensite, kerolite, dolomite and magnesite. The geology, mineralogy and geochemistry of the succession was examined by extensive field work along several trenches and a representative measured section, followed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermal, and chemical analyses.

Structurally, two distinct forms of sepiolites were distinguished by XRD: (a) well crystallized sepiolite with a 110 reflection at 12.07–12.3 Å , and (b) poorly crystallized sepiolite in which the 110 reflection occurs at 12.7–13.0 Å (denoted as sepiolite-13Å ). Differences in crystal chemistry, thermal and morphological properties of these forms, the vibrational spectra and XRD characterization of the related phyllosilicates were also documented.

Stevensite, kerolite and sepiolite were formed by direct precipitation from alkaline lake water rich in Mg and Si. Sepiolite-13Å was probably formed by transformation from precursor smectite via dissolution-precipitation, more likely during early diagenesis. Environmental conditions such as ion concentration, salinity and variations in pH may have controlled the formation of the phyllosilicates.