The orientation of the OH-vectors in hydroxyl groups of micas of different compositions, polytype modifications, and symmetry were calculated by the method of minimization of electrostatic energy. The orientations are strongly affected by the peculiarities of structures, and even slight deviations from the ideal dioctahedral periodicity can introduce a correction of as much as 10° to the value of the polar angle. Ordering of cations in octahedra lead to twisting of the OH-bond towards the octahedron with lower charge and larger dimension. The latter is less true for cation ordering in tetrahedra. Because of these factors and the dependence of the hydrogen position on the coordinates of heavy atoms, such calculations can give reliable results only if the structure has been refined with high precision. Different polytypes of micas displayed the same orientation of the OH-vectors with respect to the axes of a separate layer, if the stacking sequence did not introduce specific distortions of the 2:1 layer.

A green, Lithic Torriorthent soil derived from a celadonite-rich, hydrothermally altered basalt immediately north of the Mojave Desert region in southern California was studied to investigate the fate of the celadonite in a pedogenic weathering environment. Celadonite was found to be disseminated in the highly altered rock matrix with cristobalite, chalcedony, and stilbite. X-ray powder diffraction (XRD) showed the soil material to contain celadonite having a d(060) value of 1.510 Å, indicative of its dioctahedral nature. Very little smectite was detected in the parent material, whereas Fe-rich smectite was found to be abundant in the soil. The Fe-smectite and celadonite were identified as the sole components of the green-colored clay fraction (<2 µm) of all soil horizons. The soil clay showed a single d(060) value of 1.507 Å, indicating that the smectite was also dioctahedral and that its b-dimension was the same as that of the celadonite. Mössbauer spectroscopy showed that the chemical environments of Fe in the rock-matrix celadonite and in the smectite-rich soil clay were also nearly identical. These data strongly suggest a simple transformation of the celadonite to an Fe-rich smectite during soil formation.

Supporting evidence for this transformation was obtained by artificial weathering of celadonite, using sodium tetraphenyl boron to extract interlayer K. The intensity of the 001 XRD peak (at 10.1 Å) of celadonite was greatly reduced after the treatment and a peak at 14.4 Å, absent in the pattern of the untreated material, appeared. On glycolation of the sample, this peak expanded to 17.4 Å, similar to the behavior of the soil smectite. The alteration of celadonite to smectite is a simple transformation requiring only the loss of interlayer K. The transformation is apparently possible under present-day conditions, inasmuch as the erosional landscape position, shallow depth, and lack of significant horizonation indicate that the soil is very young.

Crystal growth theory was applied to describe edge sites of phyllosilicates. Three face configurations were found to exist. One face has one tetrahedral site per tetrahedral sheet and two octahedral one-coordinated sites per crystallographic area ac sin β, where a and c are layer dimensions and β is the angle between them. The other two faces are similar except that they have one less octahedral site which is replaced by one SiIV-O-AlVI site in this same ac sin β area. A transfer of bonding energy from the remaining octahedral site to the SiIV-O-AlVI site is believed to neutralize all edge charge on faces containing these latter sites at normally encountered pHs (pH 3–9). A similar charge rearrangement along the edges results in an apparent decrease in the permanent charge of the mineral with an increase in edge area.

On the basis of such an analysis, lath-shaped illite can be described as a very fine grained dioctahedral mica in which the apparent deficient occupancy of the octahedral sheet, presence of excess water, and measurable cation-exchange capacity may in part be the result of a large ratio of edge area to total volume, with no other chemical or structural change in the mica layers. The increasing importance of edge charge relative to layer charge produces erroneous formulae for 2:1 phyllosilicates in very fine grained samples containing fewer than 2 of 3 octahedral sites occupied by cations, on the basis of a 22-charge half cell.

A new approach to the interpretation of Mössbauer spectra of Fe3+-phyllosilicates having vacant trans-octahedra is based on (1) crystal structure simulation methods that allow for the size and the shape of a Fe3+-octahedron as a function of the nearest surrounding cations; and (2) calculations of electric field gradients (EFG) on Fe3+ in terms of the ionic point-charge model. Calculations were performed by direct summation within the region of radius ≤50 Å. Coordinates for the anions in the coordination octahedra have been assigned to take into account the nearest cationic environment. Atomic coordinates for the rest of the summation volume are those for the average unit cell. EFG calculations for cation combinations responsible for the visible quadrupole splitting Δvis in the spectra of nontronite, “red” muscovite, and celadonite have led to good agreement between Δvis and Δcalc. Computer fitting of the nontronite and celadonite spectra based on EFG calculations for the rest of the possible cation combinations suggests that the distribution of tetrahedral cations in nontronite obeys the Loewenstein rule, and in celadonite, the distribution of R3+ and R2+ over cis-octahedra is predominantly ordered, in agreement with electron diffraction and infrared spectroscopy data. The Mössbauer spectrum of one of the glauconites suggested the presence of celadonite-like and muscovite-like domains in its 2:1 layers.

Li+, Na+, Ca2+, Sr2+, Cu2+, or Zn2+-saturated samples of a cis-vacant montmorillonite from Linden, Bavaria, were heated to temperatures between 200–700°C. Half of each heated sample was subsequently autoelaved under steam at 200°C (∼1.5 MPa) to promote rehydroxylation. The smectites were characterized by cation-exchange capacity (CEC), determination of exchangeable cations, infrared (IR) spectroscopy, and thermoanalytical investigations of evolved water in a thermobalance linked with a mass spectrometer.

Changes in the montmorillonite structure and dehydroxylation behavior are related to three respective mechanisms: type of the interlayer cation, interlayer cation radius, and the movement of the interlayer cation. The migration of the smaller Li+, Cu2+, and Zn2+ ions after heating produces a strong reduction of CEC due to the Hofmann-Klemen effect before the initiation of dehydroxylation. Thereafter, the CEC of these smectites remains constant over a large temperature interval during dehydroxylation. After rehydroxylation, Cu2+ and Zn2+-rich samples release 16–23 meq/100 g of Mg2+ from the structure. No Mg2+ release is observed for the Li+-rich montmorillonite. Also the dehydroxylation behavior after rehydroxylation differs between the Cu2+, Zn2+, and Li+-rich samples. The mass curves of the evolved water during thermoanalysis of the rehydroxylated Cu2+ and Zn2+-rich smectites show a peak doublet between 480–700°C. For the Li+, Na+, Ca2+, and Sr2+-rich montmorillonites, the second peak disappeared and a third peak at ∼760°C developed after rehydroxylation. The resulting structure after rehydroxylation of all samples is celadonite-like.

The structural transformation of dioctahedral 2:1 layer silicates (illite, montmorillonite, glauconite, and celadonite) during a dehydoxylation-rehydroxylation process has been studied by X-ray diffraction. thermal analysis, and infrared spectroscopy. The layers of the samples differ in the distribution of the octahedral cations over the cis- and trans-sites as determined by the analysis of the positions and intensities of the 11l, 02l reflections, and that of the relative displacements of adjacent layers along the a axis (c cos ß/a), as well as by dehydroxylation-temperature values. One illite, glauconite, and celadonite consist of trans-vacant (tv) layers; Wyoming montmorillonite is composed of cis-vacant (cv) layers, whereas in the other illite sample tv and cv layers are interstratified. The results obtained show that the rehydroxylated Al-rich minerals (montmorillonite, illites) consist of tv layers whatever the distribution of octahedral cations over cis- and trans-sites in the original structure. The reason for this is that in the dehydroxylated state, both tv and cv layers are transformed into the same layer structure where the former trans-sites are vacant.

The dehydroxylation of glauconite and celadonite is accompanied by a migration of the octahedral cations from former cis-octahedra to empty trans-sites. The structural transformation of these minerals during rehydroxylation depends probably on their cation composition. The rehydroxylation of celadonite preserves the octahedral-cation distribution formed after dehydroxylation. Therefore, most 2:1 layers of celadonite that rehydroxylate (~75%) have cis-vacant octahedra and, only in a minor part of the layers, a reverse cation migration from former trans-sites to empty octahedra occurred. In contrast, for a glauconite sample with a high content in IVA1 and VIAl the rehydroxylation is accompanied by the reverse cation migration and most of the 2:1 layers are transformed into tv layers.

A large and representative collection of clay-size dioctahedral mica minerals differing in their chemical compositions has been studied by infrared (IR) spectroscopy in the OH stretching vibration region. Decomposition of the IR spectra in the individual OH bands has provided unambiguous identification of the band positions for each defined pair of octahedral cations bonded to OH groups. The presence of pyrophyllite-like local structural environments in samples having a deficiency of K in interlayers has been established. A set of the relationships between the OH frequencies corresponding to pairs of cations having different valency and mass has been found.

Stacking disorder in celadonite, a dioctahedral mica with Fe and Mg as major octahedral cations and which generally adopts the 1M stacking sequence, was investigated mainly by using transmission electron microscopy (TEM). The selected-area electron diffraction patterns with 0kl reflections along the [100] beam direction correspond to the 1M stacking but those along the [110], $\left[1\overline{1}0\right]$\$\end{document}, [010], [310], and $\left[3\overline{1}0\right]$\$\end{document} directions are frequently streaked along the [001]* direction or contain extra spots from twinned domains. Three-dimensional stacking analyses using sets of two high-resolution TEM images along different directions of the same area of one crystal indicate that all stacking faults involve only 180° layer rotations. These stacking faults produce greater peaks of 0kl reflections than expected in powder X-ray diffraction (XRD) patterns. Simulation of the XRD patterns indicated that 180° layer rotations occur at >10% of total interlayer regions in one celadonite specimen. The interlayer region of celadonite is characterized by a near-zero ditrigonal rotation angle, a small surface corrugation of the basal oxygen plane, and a small amount of Al substitution in the tetrahedral sheets. These features suggest that there is no preference for any of the six stacking angles around the interlayer region. The abundance of 180° layer rotation rather than ±60° and ±120° in the present specimens may be related to their ribbon-like morphologies elongated along the a axis.

Clay minerals in chilled or brecciated margins (altered glass) and massive inner crystalline parts (mesostasis) of three basalt-hawaiite bodies from Mururoa Atoll (French Polynesia) have been studied in order to compare their chemical and mineralogical compositions. Polyphase assemblages comprise di- and trioctahedral phases, both of which consist of non-expandable layers (chlorite, celadonite) and two types of expandable layers (saponite and Fe-rich smectite or ‘nontronite-like’ material). The presence of the Fe-rich clays is supported by the presence of the X-ray diffraction 060 peak at 1.51–1.52 Å and of the infrared absorption bands at 875 and 822 cm−1 (Fe3+-Al-OH and Fe3+-Fe3+-OH groups, respectively). The chemical composition of the Fe-rich smectites does not fit with the theoretical nontronite field. The layer charge averages 1 per Si4O10 making these Fe-rich smectites close to ‘celadonite-type’ clays. This could explain the presence of mixed-layer celadonite-smectite. Plotted in an M+/4Si vs. Fe/sum octahedral cations diagram, the chemical compositions of clay minerals in the mesostasis form a continuous field limited by the celadonite-high-charge nontronite-like smectite and chlorite end-members. The clay assemblages are different from those formed in hydrothermal systems or low-grade metamorphic conditions which are characterized by the sequence: saponite → randomly ordered chlorite-smectite mixed-layered minerals (MLMs) → corrensite → chlorite. The systematic presence of Fe-rich clays either in the altered chilled margins or in the massive inner parts of the basalt-hawaiite bodies (high-charge nontronite-like smectite and mixed-layer nontronite-celadonite) makes the Mururoa sea-mount a potential terrestrial analogue for Mars surface exploration.

High-resolution transmission electron microscopy (HRTEM) images of two dioctahedral micas, celadonite and cis-vacant (cv) illite, were examined in detail to understand the effects of electron radiation on their structures during image acquisition. Celadonite, a dioctahedral mica with Fe and Mg as major octahedral cations, originally has a trans-vacant (tv) octahedral sheet but the contrast in the highresolution transmission electron microscopy (HRTEM) images indicates a different cation distribution in the sheet. Furthermore, the β angle for the 1M polytype derived from the HRTEM images is ~98.5º, which is considerably smaller than that (~100.5º) reported for celadonite. In previous works, cation migration from the tv to cv-like configurations and a decrease in the β angle after dehydroxylation of celadonite/ glauconite by heating were reported. The same phenomenon, dehydroxylation and subsequent cation migration, probably occurs by electron radiation in TEM. However, the new cation-distribution models derived from HRTEM images along the [100] and [110] directions are not in agreement. On the other hand, the contrast in a number of HRTEM images from an illite specimen in which cv-illite is dominant is the same as that for the tv-dioctahedral layer. This result is also interpreted as cation migration accompanied by dehydroxylation in TEM, as reported in heated cv-illite. The increased β angle (~102.5º) from that in the natural state (101.5º) estimated from the HRTEM images also supports this interpretation. This phenomenon is a large obstacle to the investigation of phyllosilicates containing Al-rich cv and Mg,Fe-rich tv 2:1 layers, using HRTEM.

A collection of green earths belonging to traditional artists’ pigments was examined in terms of mineralogy and provenance. The studied specimens included both mineralogical reference compounds and selected commercially available artists’ pigments, and contained green micas (glauconite or celadonite), chlorite, or smectite as pigmenting agents. The samples were examined by X-ray diffraction, Mössbauer spectroscopy, infrared (IR) spectroscopy, ultraviolet-visible (UV-Vis)-near-IR diffuse-reflectance spectroscopy and voltammetry of microparticles. Particular attention was paid to the Kadaň green earth, mined until the 20th century in the West Bohemia deposit. The Greene-Kelly charge-reduction test, detailed description of non-basal diffraction patterns and characteristic vibrations in the mid-IR spectra were used to classify the major pigmenting agent of the Kadaň green earth as ferruginous smectite with separately diffracting saponite-like clusters. The smectite contains ∼15% Fe, mainly in the trivalent form, a detectable fraction of Fe in tetrahedral sites, and it is accompanied by a significant amount of Ti-bearing relict minerals due to its volcanogenic origin. On the contrary, in green micas (glauconite and celadonite) the Ti content is much smaller. Diffuse reflectance spectroscopy was found suitable for distinguishing Fe as a constituent of free Fe oxides from Fe in the clay structure. It was also found to be useful for discriminating between green micas and smectites.

Iron-bearing K-dioctahedral 1M and 1Md micas are abundant in diverse geological environments and vary in composition from illite to celadonite through Fe-illite, Al-glauconite, and glauconite. The chemistry and structural features of these micas are complex and heterogeneous, reliable diagnostic criteria are lacking, and the conventional mineralogical nomenclature is ambiguous, which complicate the identification of these mica varieties. The objectives of the present study were to reveal the structural and crystal-chemical variability in Fe-bearing, K-dioctahedral 1M micas and to define composition ranges and identification criteria for the mica varieties in the series. A collection of samples of various compositions was studied using X-ray diffraction (XRD) and Fourier-transform infrared (FTIR) spectroscopy. Analysis of the relationships between unit-cell parameters and cation composition showed that the series included four groups, namely, Fe-bearing illites, Al-glauconites, glauconites, and celadonites and each group was characterized by a specific combination of unit-cell parameters and variation ranges. The illite group contained two distinct subgroups; Fe-bearing, Mg-rich illites and Feillites; which differ in the range of cation compositions and in FTIR characteristics. The boundary between Fe-illites and Al-glauconites occurs at a unit cell b value of ~9.05 Å and at ratios of octahedral Al to total trivalent octahedral cations that range between 0.60 and 0.65. The partially overlapping cation composition and cell parameter ranges may complicate the distinction between Al-glauconites and glauconites, which can still be unambiguously differentiated using FTIR data. The dramatically different XRD and FTIR characteristics confirmed that glauconite and celadonite should be treated as separate mineral species. The distinctive features of celadonite are relatively low csinβ values and reduced |ccosβ/a| values combined with b parameters lower than glauconites, but similar to Fe-illites. Celadonites also have distinct and sharp FTIR absorption bands at specific positions in the Si-O and OH stretching regions.

The structure of dioctahedral true micas such as muscovite and celadonitic muscovite (2M1 polytype, space group C2/c) is mostly affected by variations of the octahedral Al (VIAl) content. Crystals with greater Mg, Fe substitutions (i.e. celadonitic muscovite) reduce the dimensional difference between the larger trans-oriented M1 site and smaller cis-oriented M2 octahedral site. The octahedral anionic position O4 is displaced from the center of the hexagon, defined by 031 and 032 oxygen atoms (i.e. ‘octahedral hexagon’), both on and off the (001) plane. The distance between interlayer cation A and O4 is smaller in more substituted species, thus providing different orientations of the O4−H vector, as a function of VIAl. Octahedral distances (<M2−O3> and <M2−O4> are expressed as a function of cell parameters and VIA1 content, thus allowing an approximate estimate of site dimensions. These approximations are useful when a detailed structural refinement is not available. In celadonitic muscovite, the octahedral hexagon mean edge (<O31−O32>Hex) is not significantly affected by VIA1 content. The VIA1 increase produces both a decrease in cell lateral dimensions and a distorted ‘octahedral hexagon’. The decrease in a and b is consistent with a decrease of <O31−O32>Hex, whereas the distortion of the’ octahedral hexagon’ is consistent with an increase of (<031–032>Hex), because an irregular hexagon produces a longer mean edge than a regular hexagon of equal area.

The tetrahedral mean basal edge (VI<O−O>bassal) is reduced as celadonitic substitution progresses. The tetrahedral rotation angle, α was thus found to increase from celadonite to muscovite. However, in muscovite with VIAl content between 1.8 and 2.0 atoms per formula unit (a.p.f.u.), α approaches a saturation value, thus showing a proportional increase of tetrahedral and octahedral sheet lateral dimensions. Furthermore, α variation allows a coarse approximation of the threshold VIAl content, below which celadonitic substitution may not progress.

Olduvai Gorge, Tanzania (East African Rift) exposes a 100 m thick Plio-Pleistocene sequence of dominantly volcaniclastic sediments deposited in a 50 km wide closed basin containing a playa lake. A scanning transmission electron and analytical electron microscopy (STEM/AEM) study of authigenic clay minerals in sediments from representative depositional environments in the basin (pyroclastic fan, fluvial plain, wetland, lake margin and lake basin) was undertaken to determine whether clay compositions and textures could provide unique geochemical fingerprints characteristic of source area (Plio-Pleistocene trachytic volcanics vs. Precambrian quartzose-feldspathic basement) or paleoenvironmental conditions.

Our study shows that compositional signatures obtained by clay minerals during early pedogenesis are inherited from their parent source rocks. Sediments sourced from volcanics contain highly disordered, dioctahedral smectite. Those sourced from Precambrian basement are similar, but are more Al-rich. Subsequent neoformation in the pedogenic (soil) or diagenetic (lake-margin, lake) environments results in the modification of original clay mineralogy, compositions, and textures, and unique paleoenvironmental fingerprints are acquired. Soils developed on the distal pyroclastic fan contain smectite with more Fe(III) and Mg than smectite from the proximal pyroclastic fan sediments. A trend of decreasing Al and increasing Mg content occurs in smectite compositions in samples from the fluvial to lake-margin and lake environments as a result of partial replacement of original dioctahedral Al-rich smectite by neoformed trioctahedral Mg-rich smectite (stevensite). Neoformed celadonite replaces smectite in the most saline lake sediments.

The STEM/AEM data collectively indicate that diagenesis in the saline-alkaline lake results in the replacement of Al-rich dioctahedral smectite by Mg-rich trioctahedral smectite (stevensite) and Mg- and Al-rich celadonite. Thus, determination of clay mineral compositions at a basin-wide scale provides a useful tool for interpreting the spatial distribution of depositional and diagenetic environments.

Secondary clay minerals observed in the two uppermost basalt lava flows at ODP Site 1001, in the Caribbean Sea, drilled from the large igneous province of Cretaceous age, result from low-temperature alteration processes. Alteration mainly proceeds by circulation and diffusion of sea water. Six different types of clay mineral assemblage were recognized. Initial alteration with oxygenated sea water involves Fe and K fixation, creating visible oxidation halos parallel to the sides of cracks and fissures. A saponite/ beidellite mixture, interstratified smectite-glauconite, interstratified glauconite-nontronite and Fe oxyhydroxides are obtained depending on the distance from fluid conduits. The presence of beidellite may be due to enhanced Al mobilization resulting from high fluid flux. These early minerals are cross-cut by thin veins of pure celadonite or glauconite with further vesicle infill. Late-stage alteration is typified by the formation of saponite and takes place under closed reducing conditions resulting from deposition of the sedimentary overburden.

Celadonite and glauconite samples heated at different temperatures were studied by X-ray and electron diffraction. For dioctahedral micas the in-plane component of the translation between layers (ccosβ/a), which is strongly dependent on the position of the vacant octahedral site, significantly decreases at temperatures greater than the temperature of maximum dehydroxylation. The simulation of XRD patterns from different structural models reveals the actual crystal structure of dehydroxylated samples as well as the dynamics of the structural transformations. In the nonheated state the samples consist of tv (trans-vacant) 2:1 layers. During dehydroxylation, cations migrate from cis- into trans-octahedra and have 5-fold coordination. In the averaged unit-cell the ‘residual’ anions formed after the dehydroxylation reaction occupy the former OH sites with probability equal to 0.5. The migration of octahedral cations is accompanied by the transformation of the C-centred layer unit-cells into primitive ones. In contrast to Fe, Al and Mg cations have a greater ability to migrate.

A system based on variation of the octahedrally coordinated cations is proposed for graphical presentation and subdivision of tri- and dioctahedral K micas, which makes use of elemental differences (in a.p.f.u.): (Mg – Li) [= mgli] and (Fetot + Mn + Ti – VIAl) [= feal]. All common true tri- and dioctahedral K micas are shown in a single polygon outlined by seven main compositional points forming its vertices. Sequentially clockwise, starting from Mg3 (phlogopite), these points are: Mg2.5Al0.5, Al2.167□0.833, Al1.75Li1.25, Li2Al (polylithionite), Fe22+Li, and Fe32+ (annite). Trilithionite (Li1.5Al1.5), Li1.5Fe2+Al0.5, Fe22+ Mg, and Mg2Fe2+ are also located on the perimeter of the polygon. IMA-siderophyllite (Fe2+2Al) and muscovite (Al2□) plot inside.

The classification conforms with the IMA-approved mica nomenclature and differentiates among the following mica species according to their position in a diagram consisting of mgli and feal axes plotted orthogonally; trioctahedral: phlogopite, biotite, siderophyllite, annite, zinnwaldite, lepidolite and tainiolite; dioctahedral: muscovite, phengite and celadonite. Potassium micas with [Si] <2.5 a.p.f.u. including IMA-siderophyllite, KFe22+ AlAl2Si2O10(OH)2, and IMA-eastonite, KMg2AlAl2Si2O10(OH)2 seem not to form in nature.

The proposed subdivision has several advantages. All common true, trioctahedral and dioctahedral K micas, whether Li-bearing or Li-free, are shown within one diagram, which is easy to use and gives every mica composition an unambiguously defined name. Mica analyses with Fe2+, Fe3+, Fe2+ + Fe3+, or Fetot can be considered, which is particularly valuable for microprobe analyses. It facilitates easy reconstruction of evolutionary pathways of mica compositions during crystallization, a feature having key importance in petrologically oriented research. Equally important, the subdivision has great potential for understanding many of the crystal-chemistry features of the K micas. In turn this may allow one to recognize and discriminate the extent to which crystal chemistry or bulk composition controls the occurrence of some seemingly possible or hypothetical K mica.