The low temperature synthesis of iron silicate minerals with clay structures is possible at surface temperatures only under reducing conditions. Under oxidizing conditions clay minerals could not be synthesized. Instead quartz and quartzine were found in these X-ray amorphous Fe III hydroxide-silica precipitates after 14 days at low temperatures (20° and 3°C) as well as geothite or X-ray amorphous iron hydroxides. Only from solutions containing Fe-II could the different iron-containing clay minerals be built up within days at low temperatures. The presence of Fe-II enables an octahedral layer of the brucite-gibbsite type to be formed. This is necessary for the bidimensional orientation of SiO4-tetrahedra leading to clay mineral formation. The presence of Fe2+- and/or Mg2+-ions is necessary for the formation of the Al3+- and Fe3+-containing octahedral layers. The reducing conditions were obtained in the experiments by addition of dithionite. With a high content of silica (ca. 20 ppm SiO2,7 ppm Fe) nontronite and lembergite, the di-Fe-III and tri-Fe-II octahedral, three-layer silicates, were built up in several days at low temperatures. With a lower silica content, that is, a lower Si/Fe ratio (15 ppm SiO2 and 20 ppm Fe), the two-layer silicate minerals greenalite and chamosite could be synthesized. A higher Mg content and more reducing conditions in the solutions favored the tri- as well as dioctahedral chamosite synthesis.

The conditions of formation of recent naturally formed nontronite fit well with the synthesis conditions. Chamosites in sedimentary iron ores are characterized by a low content of SiO2, between 15–30% SiO2. This low content of silica cannot be the result of primary precipitation from seawater. The iron and silica ratio in seawater or in river waters would lead to a precipitation of ~60% SiO2 in the iron hydroxide precipitates. A probable origin for chamosite iron ores, which explains the low SiO2 content, is diagenesis of the lateritic weathering crust. Indeed, investigations of recent tropical shoreline sediments and in particular their trace element content confirm that chamosite minerals have formed diagenetically from lateritic particles in reducing sediments.

Berthierine (formerly chamosite) occurs as concretions, lenses, and bands in carbonaceous, kaolinitic shale of freshwater coal-swamp deposits in Paleogene and Upper Triassic coal measures of Japan. Textural relations in thin sections of the Triassic berthierine rocks and a siderite-kaolinite-berthierine-quartz assemblage in Paleogene rocks indicate that the berthierine formed by reaction of siderite with kaolinite. The transformation of siderite and kaolinite to berthierine and quartz occurs progressively under reducing conditions between 65° and 150°C and at burial depths of 2–5 km. Utatsu berthierine is an aluminous, low-Mg variety as compared with berthierine pellets in modern marine and estuarine sediments and in ancient marine ironstones. Fe is the dominant octahedral cation with Fe2+ ≫ Fe3+. The composition of the berthierine varies between different morphological types. Utatsu berthierine transformed to ferrous chamosite when kaolinite in the host shale changed to pyrophyllite. These transformations are estimated to have occurred at ∼160°C and at a burial depth of ∼3 km.

Two distinct assemblages of authigenic phyllosilicates were distinguished in the Kremikovtsi sedimentary exhalative (SEDEX) siderite iron formation (SIF) and noted as important tracers of two styles of mineralization characteristic of this type of ore deposit. Hydrothermal-sedimentary layer silicates are represented by rare occurrences of relict microcrystalline Mg-rich berthierine with a relatively low degree of structural ordering, associated closely with framboidal pyrite as an intergranular matrix cementing sparry siderite grains; the larger silicates are also represented by the diagenetic transformation product of berthierine, chamosite. Berthierine precipitated under anoxic conditions during advanced early diagenesis after chert deposition. Hydrothermal-epigenetic phyllosilicates (berthierine, chamosite, illite-smectite (I-S), and kaolinite) from the barite-sulfide assemblage are characterized by: crystalline and undeformed habits; relatively larger particle size, low-temperature polytypes, low to no mixed layering, and a high degree of crystallinity; absence of impurities and dominant monomineralic aggregates; affiliation to initial open spaces and deposition mainly as vug fillings and linings. They formed under pronounced control by the vuggy porosity of the siderite host caused by the invasion of acid (pH = 3–5), hot (200–230°C) hydrothermal fluids probably at the stage of burial diagenesis of the SIF under relatively stable reducing conditions fluctuating near the sulfide/sulfate stability boundary $\left(\log {\text{P}}_{{\text{O}}_{\text{2}}}\cong -30\right)$. The greater Al concentration in hydrothermal solution than in seawater determines the affiliation of phyllosilicates in the Phanerozoic SEDEX SIFs to aluminous species (berthierine, chamosite) unlike low to non aluminous ones (greenalite, stilpnomelane) in the Precambrian IFs. The berthierine compositions, expressed by the Mg/Fe vs. Al/Si ratios, are a sensitive indicator of the geological conditions under which they formed (marine, non-marine, hydrothermal ore and pre-ore), thus allowing the genetic discrimination of this mineral from various localities.

Berthierine occurs as pore-linings of well crystallized laths of variable thickness in oil-sands of the Clearwater Formation, Alberta, Canada. Berthierine crystallized early in diagenesis within portions of a deltaic/estuarine complex dominated by brackish to fresh water.

Separates prepared using high gradient magnetic separation contain approximately equal amounts of monoclinic and orthohexagonal berthierine. Minor, but variable, quantities of inseparable, iron-rich impurities mainly consist of chamosite Ib and IIb, and Fe-rich smectitic clays.

Clearwater Formation berthierine has a range of chemical compositions that differ from those reported for most other berthierines. The SiO2 (27-35 wt%), Fe2O3 (5-8 wt%) and Al2O3 (16-18 wt%) contents for Clearwater Formation berthierine fall between values normally reported for berthierine and odinite. The average structural formula of five samples studied in detail is (Fe2+1.01Al0.82Mg0.46Fe3+0.28 Mn<0.01□0.43)(Si1.74Al0.26)O5(OH)4, where □ represents vacancies in the octahedral sheet. The large number of vacancies in the octahedral sheet implies a di-trioctahedral character for this clay. Our results also suggest that a series of compositions can occur between ideal berthierine and odinite end-members.

Berthierine has been preserved within the Clearwater Formation because temperatures during diagenesis did not exceed 70°C, and perhaps also because hydrocarbon emplacement limited subsequent transformation of berthierine to other phases, such as chamosite. Intense, early diagenetic, microbial activity and/ or the strongly reducing environment created by later emplacement of hydrocarbons may be responsible for the Fe2+/Fe3+ ratio of the berthierine. Because of these conditions, this ratio may have changed since initial clay crystallization. The Clearwater Formation occurrence of grain-coating Fe-rich clays provides valuable insights into possible relationships between the Fe-serpentine minerals, odinite and berthierine, and supports an important role for these phases as precursors to the grain-coating and pore-lining Fe-chlorite (chamosite) that is so common in ancient sandstones, including many hydrocarbon reservoirs.

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.

Several generations of chamosite, including a red variety, occur in the Ordovician hydrothermalized oolitic ironstone from Saint-Aubin-des-Châteaux (Armorican Massif, France). Their chemical re-examination indicates a low Mg content (0.925 < Fe/(Fe + Mg) < 0.954), but a significant variation in IVAl. Minor vanadium is present at up to 1.1 wt.% oxide. Variations in IVAl, the vanadium content and the colour of chamosite are related to the hydrothermal reworking of the ironstone. Taking into account other published data, the ideal composition of chamosite is (Fe5–xAl1+x)(Si3–xAl1+x)O10(OH)8, with 0.2 < x < 0.8 (0.2: equilibrium with quartz; 0.8: SiO2 deficit). The red chamosite (IIb polytype) has a mean composition of (Fe3.87Mg0.23Mn0.01□0.07Al1.74V0.07)(Si2.33Al1.67)O10(OH)8. This chamosite is strongly pleochroic, from pale yellow (E || (001)) to deep orange red (E ⊥ (001)). Visible–near-infrared absorbance spectra show a specific absorption band centred at ~550 nm for E ⊥ (001), due to a proposed new variety of Fe/V intervalence charge-transfer mechanism in the octahedral sheet, possibly Fe2+ – V4+ → Fe3+ – V3+. While the formation of green chamosite varieties is controlled by reducing conditions due to the presence of organic matter as a buffer, that of red chamosite would indicate locally a weak increase of fO2 related to oxidizing hydrothermal solutions.

Within the Variscan basement of Sardinia (Italy), two main Fe concentrations occur in the low-grade metamorphic tectonic units: (1) an uppermost-Ordovician oolitic ironstone of shallow anoxic water environment; and (2) a concentration of Fe oxyhydroxides lying on a palaeosurface. Two sets of samples were picked from the marine ironstone and from the continental Fe concentration following stratigraphic criteria. Chemical analysis, X-ray diffraction, scanning electron microscopy-energy dispersive X-ray analysis and thin-section studies were performed on 34 samples.

Marine ironstones formed under a highly reducing, anoxic, non-sulphidic methanic environment, and their Fe phases are chamosite, siderite and magnetite. Detrital chlorite and illite, produced during physical weathering, were chamosite precursors. Using the V/Cr proxy, an emergence stage that caused a transition to an oxic environment is documented. In contrast, continental ironstones formed under oxic conditions and the dominant Fe phase is goethite, which can adsorb Zn2+ and U6+. Unexpected negative Ce anomalies occur in this set of samples, suggesting that the oxyhydroxides originated from Ce-depleted solutions. Although the ironstones of Sardinia formed in different environments (marine vs. continental) and under contrasting climatic conditions (sub-glacial vs. tropical) they share similar geochemical features. These dramatic palaeoenvironmental differences did not result in large differences between the geochemistry of the chemical sediments.

The chlorite-group mineral chamosite occurs in nanocrystalline form (~200 nm grain size) as a naturally occurring clay in the Quaternary marine sedimentary deposits near Kudiamozhi, Tuticorin District, Tamil Nadu, India; samples were used in this study as a reusable catalyst. The clay has the usual alternating tetrahedral-octahedral-tetrahedral silicate/aluminate/silicate layer structural arrangement (sometimes called the 2:1 silicate or talc layer structure). The interlayer and the t-o-t layer are bound together by both electrostatic and hydrogen-bonding forces. This natural clay catalyst has been well characterized by various techniques such as Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), X-ray diffraction (XRD), temperature programmed desorption (TPD), thermal analysis and BET surface area measurements (Sreedhar et al., 2009); it has been utilized for various organic transformations such as acylation of alcohols and amines, cyclization of arylaldehydes with O-phenylenediamines and C-O bond formation reactions.

Mössbauer spectroscopy and electron microscopy were combined to study one Al-poor anthophyllite and one Al-rich gedrite. TEM show that Al-rich gedrite is not homogeneous and that the complexity of its Mössbauer spectrum is due to sub-microscopic intergrowth of chlorite and lizardite.