A monoclinic IIb-2 clinochlore from Washington, D.C., contrary to previous studies, is primarily a ferroan rather than a ferrian chlorite. Disorder of tetrahedral Si,Al cations is indicated because of unsuccessful structural refinements in subgroup symmetries. The true space group is C2/m. Slight ordering of Mg, Fe2+, and Fe3+ over octahedra M(l) and M(2) within the 2:1 layer (mean M-O,OH = 2.092 and 2.084 Å, respectively), complete ordering of trivalent Al into the centrosymmetric octahedron M(4) of the interlayer sheet (M-OH = 1.929 Å), and ordering of primarily divalent cations (Mg and Fe) into the two interlayer M(3) octahedra (M-OH = 2.117 Å) exist. The excess of negative charge above unity due to tetrahedral substitution of Al for Si (1.378 atoms) is compensated entirely within the octahedral sheet of the 2:1 layer.

Ordering of a trivalent cation into one octahedron in the interlayer should be universal for all stable trioctahedral chlorites. In this specimen the ordering is due to (1) minimization of cation-cation repulsion by layer offsets which provide more space around the trivalent element, and (2) energy minimization by localization of the source of positive charge on the interlayer sheet in one octahedron rather than two. In other structures or for different compositions additional factors can be important also. Most chlorites of the IIb and Ib (β = 90°) types are expected to show disorder of the tetrahedral cations. The b positioning of interlayer and layer provides no preferential driving force for concentration of Si and A1 in any tetrahedron as a consequence of the expected ordering of the interlayer cations. The monoclinic IIb-2 polytype is less abundant in nature than the triclinic IIb-4 and IIb-6 structures, because only half as many possible superpositions of layers exist that will produce monoclinic symmetry. Crystallization factors must also be important, because the IIb-2 chlorite is much less abundant than predicted by this purely geometrical argument.

The crystal structure of a natural, ordered IIb-4 triclinic clinochlore has been refined in space group C1̄ from 4282 unique X-ray intensity measurements of which 3833 are greater than 3 times the statistical counting error (3σ). Unit cell parameters are a = 5.3262(6) Å; b = 9.226(1) Å; c = 14.334(3) Å; α = 90.56(2)°; β = 97.47(2)°; and γ = 89.979(9)°, which represents the greatest deviation from mono-clinic symmetry yet recorded for a triclinic chlorite. The final weighted R is 0.059 for reflections with I > 3σ and 0.064 for all reflections. The chemical formula is (Mg0.966Fe0.034)MI(Mg0.962Fe0.038)M22(Si2.96Al1.04)O10 (OH)2(Mg0.996Fe0.004)M32(Al0.841FeIII0.102Cr0.004Ti0.004)M4(OH)6, which is consistent with electron microprobe (EMP), wet chemical analyses, Mössbauer spectroscopy and X-ray structure refinement. The high degree of ordering of the divalent versus trivalent octahedral cations in the interlayer is noteworthy, with FeIII and Al in M4 and virtually no Fe in M3. In the 2:1 layer, M1 and M2 each contain similar amounts of Fe. The 2 tetrahedral sites have nearly identical mean oxygen distances and volumes, and thus show no evidence of long-range cation ordering.

The “modified chlorite structure” forms by the dehydroxylation of the interlayer octahedral sheet of magnesian chlorite at around 500°C and results in a structure with a basal spacing near 27 Â (Brindley and Chang 1974). This process involves drastic textural modifications as indicated by gas adsorption experiments which reveal the formation of structural micropores. Infrared spectroscopy as well as thermogravimetry and mass spectrometric analysis show that these micropores are filled with molecular atmospheric water, carbon dioxide, nitrogen, argon and hydrocarbons which condense once the samples cool down. A high temperature treatment is needed in order to release the different phases. A heterogeneous dehydroxylation mechanism is proposed in which micropores are formed in donor regions and magnesium and oxygen are concentrated in acceptor regions. This leads to a 27 Å structure with micropore zones and enriched interlayer oxide zones alternating along the z-axis of the mineral.

The method for prediction of Gibbs free energies of formation, based on the parameter ΔGO=Mz+(clay) characterizing the oxygen affinity of the cation Mz+, on the smectites, considered as hydrated clay minerals, has been used for micas and brittle micas, and yielded underestimated values. This method of prediction can be improved by a new set of parameters ΔGO=Mz+(clay), characterizing the electronegativity of a cation in a specific site (interlayer, octahedral, tetrahedral in the 10 Å minerals), determined by minimizing the difference between experimental Gibbs free energies and calculated Gibbs free energies of formation from constituent oxides. By considering the crystal structure of 10 Å and 14 Å minerals, and assuming the same electronegativity of cations, ΔGO=Mz+(o), in the octahedral sheets, an attempt is made to determine the electronegativity of cations in the brucitic sheet, ΔGO=Mz+(b). The results indicate that this prediction method compared to other determinations, gives values within 0.25% of the experimentally-estim ated values. The relationships between ΔGO=Mz+(clay) corresponding to the electronegativity of a cation in the interlayer, octahedral, tetrahedral or brucitic sites and known ΔGO=Mz+(aq) were thus determined, allowing the determination of the electronegativity of transition metal ions and trivalent ions in each of the four sites and consequently contribute to the prediction of Gibbs free energies of formation of different micas and chlorites. Examples are given for low-Fe clinochlore whose solubility is measured experimentally and the results appear excellent when compared with experimental values.

The hydrothermal stabilities of a low-Fe clinochlore and a high-Mg chamosite, in the presence of kaolinite, were investigated recently at T ⩽ 200°C and $P_{\text{v}}=P_{{\text{H}}_{\text{2}}\text{O}}$ (Aja and Small, 1999; Aja and Dyar, 2002). Standard state thermodynamic properties ($S_{298}^0$, ${\Delta }_f{H}_{1,298}^0$ and ${\Delta }_f{G}_{1,298}^0$) have been obtained for the two chlorites whose structural formulae are (${\text{Al}}_{2.33}{\text{Fe}}_{1.00}^{2+}{\text{Fe}}_{0.14}^{3+}{\text{Ca}}_{0.02}{\text{Mn}}_{0.01}{\text{Ni}}_{0.02}{\text{Cr}}_{0.01}{\text{Mg}}_{8.40}{\alpha }_{0.07}$) (Si5.66Al2.34)O20(OH)16 and (${\text{Fe}}_{0.60}^{3+}{\text{Fe}}_{5.43}^{2+}{\text{Mg}}_{2.30}{\text{Al}}_{2.98}{\text{Mn}}_{0.05}{\text{Ca}}_{0.03}{\text{Zn}}_{0.01}{\alpha }_{0.60}$)(Si5.63Al2.37)O20(OH)16. For the low-Fe clinochlore, the respective thermochemical properties are 430 J mol−1 K−1, −8770.64±35.24 kJ mol−1, and −8120.54±32.63 kJ mol−1. ${\Delta }_f{H}_{1,298}^0$, ${\Delta }_f{G}_{1,298}^0$ and ${\text{S}}_{298}^0$, similarly obtained for the Windsor chamosite are −7851.29±23.14 kJ mol−1, −7271.01±21.43 kJ mol−1 and 668±5 J mol−1K−1, respectively. Ideal site-mixing models of chlorite composition, along the chamosite-clinochlore binary, fail to model satisfactorily these chlorite-fluid equilibria only at lower temperatures (T <175°C). The magnitudes of the excess thermodynamic properties calculated for these chlorites, within the ternary clinochlore-daphnite-sudoite system, suggest significant deviations from ideality.

The purpose of this study was to investigate the structural and chemical modifications of phyllosilicates that occur under natural conditions, using the progressive deformation of chlorite (sudoite) present in quartz-rich veins from the Internal Zone of the Rif range (Morocco) as the model system. Signs of chlorite deformation include kinks, chevron-like folds, and fractures. The samples also contain later, undeformed grains, which sealed the fractures or grew with (001) perpendicular to the compressive stress. Deformation-induced structural changes consist mainly of basal cleavages associated with ordered replacement of brucite sheets by hydrated layers, thus leading to irregular microdomains of mixed-layer chlorite-vermiculite and sudoite. Such structural modifications represent a mechanism for accommodating the compressive stress. Structural changes were accompanied by minor chemical ones, which lead from di,tri-chlorite (sudoite) to phases with a more trioctahedral character (mixed-layer chlorite-vermiculite). The hydration reaction occurred throughout a topotactic replacement of the pre-existing sudoite grains. Later, undeformed grains consist of mixed-layer chlorite-vermiculite intergrown with retrogressive kaolinite and minor Fe oxide, and are interpreted as having formed through a dissolution-precipitation process, during deformation. Retrogression of sudoite probably occurred during the latest stage of exhumation, in low-temperature conditions.

Natural and synthetic micas have been used widely as substrates to study biological systems; but, as in the case of negatively charged DNA, anionic charge repulsion may render micas a less than ideal templating surface for many biological systems. The purpose of this study was to investigate the potential for the chlorite clinoclore, which contains a positively charged interlayer octahedral sheet, to serve as a substrate for DNA adsorption. The relationships between clinochlore cleavage characteristics, in terms of nano-morphology, and surface potential are investigated, as are its average crystal chemistry and topology. That the structural features of clinochlore can be used successfully to condense, order, and self assemble complex biomolecules, such as DNA is also proven.

A natural IIb-4 clinochlore [$C\overline{1}$\$\end{document} symmetry, unit-cell parameters a = 0.53301(4); b = 0.92511(6); c = 1.4348(1) (nm); α = 90.420(3); β = 97.509(3); γ = 89.996(4) (°)] with chemical composition $\left({\text{Mg}}_{1.701}{\text{Fe}}_{0.245}^{2+}{\text{Ti}}_{0.004}{\text{Al}}_{0.998}{\text{Cr}}_{0.052}^{3+}\right){\text{Mg}}_3\left({\text{Si}}_{2.939}{\text{Al}}_{1.015}{\text{Fe}}_{0.046}^{3+}\right){\text{O}}_{10}\left({\text{OH}}_{7.913}{\text{F}}_{0.087}\right)$\$\end{document} was selected. The octahedral sites of the silicate layer (<M(1)−O> = 0.2080 nm and <M(2)−O> = 0.2081 nm) are equal and occupied by Mg, whereas the octahedral sites in the interlayer M(3) and M(4) (<M(3)−O> = 0.2088 nm and <M(4) − O> = 0.1939 nm) show different sizes and are mostly completely occupied by divalent (Mg2+ and Fe2+) and trivalent (Al3+) cations, respectively.

The clinochlore cleaved surface is present in two forms: (1) the stripe type (0.40 nm in height, up to several micrometers long and ranging from some nanometers to a few microns in lateral size); and (2) the triangular type (0.40 nm in height). Both features may result either from interlayer sheets whose cleavage weak directions are related to the different M(3) and M(4) site occupancy, or from weak interlayer bonding along specific directions to the 2:1 layer underneath. The cleaved surface, particularly at the cleaved edges, presents high DNA affinity, which is directly related to an average positive surface and ledge potential.

The hydrothermal reaction of kaolinite in the system Na2O-K2O-(MgO)-Al2O3-SiO2- H2O has been investigated at 200 and 300ºC. The study of the solid products indicates that, at 200ºC, disordered illite was the first phase formed, which evolved at increasing run times towards well ordered illite and analcime. After longer reaction times illite and kaolinite were the sole phases identified by XRD. The b parameter of the illites increased at longer reaction times, from 9.05 to 9.08 Å. Study by TEM/AEM revealed the presence of surface chlorite-like layers, covering the illite packets, however. The trend observed in the products of the reaction at 300ºC was similar, except for the presence of boehmite or pseudoboehmite at the higher temperature. The values of the bparameter of illite, of the order of 9.12 –9.16 Å, indicate that illites formed at 300ºC have a more trioctahedral character. The results obtained also indicate that Mg determines which product will be formed, Kand Na-zeolites and Al-rich illites being the phases formed in the absence of Mg.

Lizardite-1T crystals from Gew-graze at the Lizard, Cornwall, of an apparent composition (Mg2.94Fe0.03Al0.03)(Si1.97Al0.03)05(OH)4, have been observed to contain 2–5% of thin interstratifications of clinochlore when investigated by analytical transmission electron microscopy (TEM). The clinochlore is usually only a few unit layers thick but has an extensive lateral dimension parallel to the lizardite layers. Analytical TEM confirms the existence of very low-Al lizardite with a planar structure interstratified with occasional thin units of clinochlore containing substantial Al. Compositionally, such clinochlore (invisible by X-ray diffraction) interstratified throughout the lizardite crystals, could account for most of the Al present. We suggest that an occasional influx of Al causes the nucleation and growth of clinochlore at the expense of lizardite. The possibility of clinochlore contributing to the measured Al content in lizardite samples highlights the need for future investigations of Al-bearing serpentines to include careful examination and interpretation using imaging and analysis by TEM.

It has crept into serpentine discussions that lizardite cannot form without the coupled substitution of Al to relieve the misfit between the sheets of octahedra and tetrahedra. The lizardite at Gew-graze is almost Al-free, forms well-crystallized planar crystals and demonstrates that Al is not an essential element for lizardite crystallization.