Differences in equilibration rates among crystals of different sizes may be used to deduce paleofluid changes over time if the crystal-growth mechanism is known. To explore isotopic equilibration rates as a function of illite growth, we studied B-isotope changes during illitization of smectite. Montmorillonite (<2.0 µm SWy-1, K saturated) was reacted with aqueous boric acid (1000 ppm B) at 300°C, 100 MPa in sealed Au capsules (1:1 fluid:mineral ratio). The initial fluid was 0‰ (NBS 951 standard) but after R1 ordering occurred (65 days of reaction) the fluid was changed to −7‰ in order to examine the rate of isotopic re-equilibration. Samples were taken intermittently throughout the experiment. Each aliquot was NH4 exchanged and size separated into fine (<0.2 µm), medium (0.2–2.0 µm) and coarse (>2.0 µm) fractions. The isotopic composition of B in the tetrahedral sheet was then measured for comparison with the predicted equilibrium values.

The fine fraction showed equilibrium isotope ratios within 10 days, indicating that small, newly nucleated crystals precipitate in equilibrium with the fluid under supersaturated, closed conditions. These fine-fraction minerals did not re-equilibrate when the fluid was changed. The medium fraction gradually equilibrated with the initial fluid as illite grew to values >50%, but did not re-equilibrate with the later fluid. The coarse fraction was slow to begin recrystallization, perhaps due to dissolution kinetics of large crystals or the presence of detrital contaminants. However, it showed the fastest rate of isotopic change with crystal growth after R1 ordering. We conclude that at 300°C, the initial B–O bonds formed in illite are stable, and isotopic re-equilibration only occurs on new crystal growth. Therefore, different isotope ratios are preserved in different crystal size fractions due to different rates of crystal growth. Large crystals may reflect equilibrium with recent fluid while smaller crystals may retain isotope compositions reflecting equilibrium with earlier fluids.

The porosity of a propylitized granite from Charroux (France), with no fractures or sealed fractures, increases by more than four times from the unaltered (0.3%) to the altered rock (1.4%). This evolution results from several local porosity modifications which occur at different scales in the rock: (1) at the core scale, from 10−1 to 10−5 m, where rock porosity changes as a function of rock-forming mineralogical composition; (2) at the mineral scale, from 10−3 to 10−7 m, where porosity depends both on the nature of the rock-forming mineral and its clay mineral alteration. Mineralogical and porosity data collected from the granite using a mineralogical map (after chemical staining and scanning electron microscopy images combined with autoradiographs) indicate that (1) the ferromagnesian rock-forming minerals — biotite and magnesiohornblende — act as the main porosity source in the unaltered granite, and (2) the nature of the clay minerals replacing rock-forming minerals in the altered granite appears to control the porosity value through two major alteration processes: chloritization and phengitization which affect the ferromagnesian minerals and produce non-porous chloritic and porous phengitic areas, respectively, at the studied scales. The observation that incipient porosity formation in granites is strongly linked to the pathway of ferromagnesian silicate alteration and subsequent clay mineral formation underlines the need to study parent-rock texture and mineralogy and their effects on subsequent near-surface weathering of granites.

The Güzelöz-İncesu Plateaus are situated in the central and eastern parts of the Cappadocian volcanic province (central Anatolia). This province contains many ignimbrite levels, andesite, basalt intercalated with several paleosols, calcrete, carbonate, fluvial sediments, diatomaceous clayey sediments and pyroclastic sedimentary levels. The presence of mottling, sesquioxide, root traces, rhizoids and burrows in continuous, finely bedded and laminated sediments, paleosols, calcrete, the occurrence of bone- and teeth-bearing reworked pyroclastic materials, and the description of the lithofacies in the study area indicate fluvial and shallow-lake environments. These environments are dominated by smectite and illite, with traces of kaolinite, associated mainly with plagioclase, K-feldspar, quartz, calcite, opal-CT, pyroxene (diopside, rare hypersthene), and locally trace amounts of gypsum and sepiolite. Smectite predominates in paleosols and calcrete units, and generally increases upwards in the profiles, coinciding with a gradual increase in the degree of alteration. Partial to complete alteration of plagioclase, K-feldspar, pyroxene and partial devitrification of glass-shard particles in pyroclastic rocks, development of microsparitic to sparitic cement comprising euhedral rhombic calcite crystals between irregular clay nodules in paleosol and calcrete samples, along with the occurrence of dogtooth-type sparitic crystals in fractures, desiccation cracks and geopetal-type fenestrae, indicate alternating periods of drought and wet, resulting in the development of paleosols and calcretes. Micromorphological development of spongiform smectite on mainly relict feldspar and, locally, on glass shards, indicates an authigenic origin, whereas illite formed either authigenically or by conversion of smectite to illite-smectite.

Soils developed on Quaternary fluvial fill terraces in the humid tropics of Costa Rica display progressive changes in mineral assemblage, chemical composition and particle size with age. Clay minerals from B horizons of active floodplains are predominantly smectite with lesser amounts of disordered kaolinite. B horizons in 5 to 10 ka soils consist of sub-equal amounts of smectite and disordered kaolinite, and soils on 37–125 ka terraces consist of disordered kaolinite with only traces of smectite. The composition of the smectite, as determined by EDX scans of smectite-rich pore space, is [(Mg0.2,Ca0.1)(Fe0.6Al1.4)(Si3.6Al0.4)O10(OH)2], consistent with ferruginous beidellite.

Bulk mineral assemblage varies from a smectite-plagioclase-augite-quartz-magnetite assemblage in ⩽ 10 ka terrace soils to a disordered kaolinite-goethite-hematite-quartz-magnetite assemblage in ⩾37 ka terrace soils. Leaching results in rapid loss of soluble base cations and residual concentration of Ti and Zr indicates mass losses of ∼50% by chemical denudation by 125 ka. Plots of terrace age vs. various measures of clay mineralogy, chemical composition, and particle size produce parabolic curves consistent with rapid chemical weathering pre-37 ka and slower to imperceptible rates of change from 37 to 125 ka. For some pedogenic properties, particularly particle size and concentrations of base cations and Zr, soils appear to reach steady-state conditions within 37 ka.

These results were applied to interpretation of landscape evolution in this tectonically active region by: (1) facilitating identification of two Holocene (5 ka and 10 ka) terraces on the Esterillos Block 5–30 m above sea level (masl), and two Pleistocene terraces ⩾ 125 ka on the Parrita Block 30 masl, and, in turn, (2) documenting uplift rates as high as 4.4 m/ka between 37 and 10 ka on the Esterillos Block, and as low as 0.1 m/ka over the past 125 ka on the adjacent Parrita Block. These findings are consistent with previous work indicating that the subduction of anomalous bathymetric features at the Middle America Trench is having a significant impact on fore-arc dynamics and topography over relatively short geological time periods and spatial scales.

The zeolites and coexisting minerals of the silicic vitric tuffs in the Alaçatı (Çeşme) area, west of İzmir (Turkey), were studied. Mordenite is the most abundant zeolite in tuffs of the Alaçatı area and usually coexists with clinoptilolite-heulandite, smectite and calcite. Opal-CT was identified by means of its crystal morphology and EDX spectrum. Scanning electron microscopy (SEM) revealed the relative age relationships between the zeolites and coexisting minerals, namely mordenite, clinoptilolite-heulandite, smectite, calcite, and, in addition, opal-CT. Smectite consistently crystallized earlier than any of the zeolites, and it occasionally coats the outer walls of some of the vitric material. The zeolites are commonly located on the smectite, although some mordenites were observed to be in direct contact with glass shards that lacked a smectite coating. Clinoptilolite-heulandite formed after smectite and before mordenite. Opal-CT is seen to postdate both smectite and needle-shaped mordenite. Calcite was probably the latest mineral to crystallize in the Alaçatı tuffs. The zeolites in the tuffs of the Alaçatı area formed by dissolution of silicic vitric tuffs by Na- and Ca-rich thermal waters which passed through the fracture zone. The appearance of zeolites together with smectite along this zone may be attributed to a semi-open system which subdivided into smaller closed systems. Small changes in the pH and chemical composition of the thermal waters during alteration produced the corrosion effects observed by SEM. Small amounts of clinoptilolite-heulandite were corroded prior to crystallization of coexisting mordenite. The different compositions of the thermal waters were probably inherited from water that resulted from mixing of thermal and groundwaters.

The dissolution of brucke, Mg(OH)2, on the (001) surface was investigated using in situ atomic force microscopy in solutions at near-neutral pH. Dissolution proceeded by the formation of crystallographically oriented triangular etch pits with monolayer step and expansion of the pits. The sides of the triangle are parallel to the [100], [110] and [010] directions of the brucite structure, and the orientation of lines from the center of the triangle to the three apices are along the [210], $[\overline{1}10]$$[\bar 110]$ and $[\overline{1}\overline{2}0]$$[\bar 1\bar 20]$ directions. This orientation may produce pit edges where OH groups coordinate to two Mg2+. Although triangular etch pits with monolayer depth formed mostly at random on the (001) surface, concentric pits penetrating several layers were also observed. Etch pits with spiral steps were rarely observed. Coalescence of the pits resulted in stranded terraces that diminished in size rapidly and formed a rounded irregular form. The step-retreat velocity around the triangular pit is 0.015–0.04 nm/s at pH 5–8. The retreat velocity around the stranded terraces was about three times more rapid than that around the triangular etch pits.

Todorokite is a common Mn oxide (with a tunnel structure) in the Earth surface environment, and can be obtained by hydrothermal treatment or refluxing process from precursor buserite with a layered structure. Several chemical reaction conditions for the phase transformation from Na-buserite to todorokite at atmospheric pressure were investigated, including temperature, pH, crystallinity of precursor Na-buserite, the amount of the interlayer Mg2+ of the Mg-buserite and clay minerals. The results showed that the conversion rate and crystallinity of todorokite decreased with falling temperature, and Mg-buserite could not be completely transformed to todorokite at lower temperatures (40°C). The poorly crystalline Na-buserite could be converted into todorokite more easily than highly crystalline Na-buserite. Todorokite can be prepared at pH 5–9, but the rate of conversion and crystallinity of todorokite did vary with pH in the order: neutral ≈ alkali > acidic. The conversion rate of todorokite decreased with decreasing interlayer Mg2+ content of the Mg-buserite. The presence of montmorillonite or goethite slowed the formation reaction of todorokite in the refluxing process, and the reaction time was prolonged when the amounts of those minerals were increased.

This paper presents a novel concept in the thermodynamic derivation of phase diagrams for clay minerals that incorporates fuzzy transition zones. This new technique yields phase diagrams that have graded (fuzzy) zones of mineral occurrences and includes compositional variability within mineral groups. For the construction of these diagrams, 170 minerals belonging to nine different subgroups were used, based on a fuzzy mathematical description of their ‘grades’ or ‘belonging-ness’. Standard free energies of formation of all the minerals were derived and all possible pairs of mineral equilibria were evaluated. Relative intensities of mineral occurrences were determined and membership values of each type of mineral at various zones in a 2D or 3D space were graphically represented. Computations and graphical representations were carried out using programs developed in Mathematica. Diagrams were derived for 25°C, 1 bar with a solution phase containing Si(OH)4, K+, Na+, H+, Ca2+ and Mg2+ under conditions of gibbsite, goethite and ferrous oxide saturation. The resulting diagrams, unlike conventional phase diagrams, show multimineral assemblages, with varying occurrences of different minerals and provide a realistic representation of clay mineral occurrences formed by surface geochemical processes. They show that on the Earth’s surface, only montmorillonite can almost completely predominate the inorganic phase followed by kaolinite, illite and beidellite. Nontronite, glauconite, celadonite and vermiculite would not be neoformed in substantial amounts. A general conformity of derived phase equilibria with experimentally observed equilibria is also observed.

Basic Al chloride, sulfate and nitrate were prepared by hydrolysis of Al chloride followed by precipitation with a Na sulfate solution, then re-dissolution in a Ba nitrate solution. The three laboratory-synthesized oligomers and solid, commercial chlorhydrol were characterized by X-ray diffraction, 27Al nuclear magnetic resonance and scanning electron microscopy coupled with energy dispersion spectroscopy analysis. The results showed that basic Al chloride contained unknown crystalline Keggin species. In commercial chlorhydrol, Al13 species were present in small amounts aside from the monomeric species. Basic Al nitrate or sulfate contained exclusively Al13 species. Pillaring a raw montmorillonite with different Al complexes in very concentrated media using both the clay and the oligomer in the solid state led to different pillared structures. Characterization by transmission electron microscopy, nitrogen adsorption, and thermogravimetric analysis of the materials obtained shows that pillaring with sulfate or chloride oligomers gave very heterogeneous pillared clays. Although basic Al nitrate and commercial chlorhydrol give better ordered and well organized pillared clays, the stacking obtained with chlorhydrol is greater.

The Bracarense ceramics are characterized by a fine, pale yellow paste covered with a brownish yellow slip. The name is derived from Bracara Augusta, the Roman town located in the north of Portugal, where this type of ceramic paste was first found and identified. Various forms with the same type of paste occur, such as imitations of sigillata, terra sigillata and thin walls from the Augustus-Tiberius period, and common ware. Later, similar ceramics were also found in other archeological sites, e.g. Aquis Querquennis (Galiza, Spain), which question the location of the production center of this type of ceramic paste.

Mineralogical and chemical analyses showed that the majority of the Bracarense shards studied differ from the common ware of the Braga region. Despite minor differences, the Bracarense shards collected in Aquis Querquennis have the same geochemical pattern as those found in Bracara Augusta, i.e. they appear to have been manufactured with the same clay type. The firing products found indicate a kaolin character of the source clay, and point to firing temperatures near 900°C. The Aquis Querquennis shards have greater Br contents, which can be explained by use-wear and/or post-depositional processes, as this site is located in a thermal-water region.