The sedimentology and mineralogy of a 2.5 m core from a palygorskite deposit of the Miocene Hawthorne Formation, southern Georgia is described. The lithology involves laminated clay-rich sediment composed of ∼90% clay and 10% sand, with six clay-pebble layers present. Sand to pebble-size clasts of phosphate material are common throughout the core. The sand laminations are probably flood-related and the clay-pebble layers are storm deposits, with the pebbles being derived locally from subaerial environments. Phosphate clasts are reworked bone material.

The sands are quartz-rich and are subarkosic in composition with average quartz counts of 86.50% and average total feldspar counts of 11.50%. Heavy minerals observed include orthopyroxene, clinopyroxene, amphibole, zircon, rutile, garnet, tourmaline, kyanite, muscovite, biotite, spinels and opaques. Palygorskite fibers dominate the clay-size fraction of the samples and comprise ∼80–90% of sample material with smectite comprising the remainder. Hydroxylapatite comprises ∼3% of sediment volume and occurs as individual euhedral hexagonal crystals and as clusters of crystals.

Investigation of this core suggests that the palygorskite deposit represents a dynamic system with regular flooding and storm deposition being common. Mineral composition of sands may be useful for stratigraphic correlation of palygorskite deposits in the Apalachicola Embayment. This study supports the general environmental interpretations of previous workers for the palygorskite deposits of southern Georgia, but provides greater detail.

A microtexture analysis by TEM and AFM of palygorskite deposits from the Hawthorne Formation, southern Georgia is given. Palygorskite is the dominant mineral comprising an average of 65–70% of the sample volume with smaller volumes of smectite, illite and kaolinite. Morphologic observations indicate that the palygorskite formed in an unconfined environment, such as in the water column or in open-pore space. Some palygorskite textures appear to be secondary growths filling voids. An unusual texture is observed where smectite or illite-smectite (Reichweite, R = 0) form epitaxially on detrital illite and kaolinite particles. Oxides of Fe and Ti are common, and authigenic cassiterite is present but rare. Apatite is a common trace mineral in these sediments and occurs in a variety of textures. Apatite occurs as clusters which are believed to be small fecal pellets. These clusters have been partially dissolved and recrystallized and the crystals in the clusters are 50–100 µm in diameter. Other apatite crystals occur either as single crystals or in clusters that are not associated with fecal pellets.

The textural data of this study suggest that there was an evolving and complex mineralogical and geochemical system during and after deposition of the palygorskite deposits in the Hawthorne. The epitaxial overgrowths of smectite on detrital illite and kaolinite particles indicate an intermittent stratified water column occurring in the system. Freshwater was introduced into the system from the northeast of the Apalachicola embayment and overrode more saline water in the southwest portion of the embayment. The results of this study are consistent with previous environmental interpretations and provide additional details.

Halloysite and kaolinite occur in gneissic weathering profiles developed under a temperate climate in the Leucogia area of NE Greece. X-ray diffraction analyses of samples from three profiles of partially weathered gneisses have revealed that kaolinite becomes more abundant than halloysite with increasing intensity of the decomposition processes. To resolve the genetic relationship between halloysite and kaolinite, microtextures were examined by scanning electron microscopy using polished thin-sections and freshly exposed fracture surfaces, and their chemical compositions were determined using an analytical scanning electron microscope fitted with energy dispersive and wavelength dispersive spectrometers. Different morphological forms of halloysite and kaolinite were detected within the same rock mass. In the earliest stage of weathering, spheroidal aggregates consisting of microcrystalline halloysite are formed on the plagioclase surface. With progressive weathering, spheroidal halloysite converts to tubular halloysite. As weathering advances, tubular halloysite converts to platy halloysite, which in turn converts to kaolinite. Halloysite and kaolinite may coexist in the upper parts of the profiles. Electron microprobe analyses of spheroidal, tubular and platy halloysite and kaolinite show that the chemical composition of the various forms indicate a progressive Fe enrichment and Al depletion with advancing kaolinization, from VIFe0.08VIAl3.70 a.p.f.u. in spheroidal halloysite through VIFe0.29VIAl3.50 in platy halloysite to VIFe0.53VIAl3.32 in newly formed kaolinite. Final-stage, book-type kaolinite approaches its ideal chemical composition (VIFe0.04VIAl3.95). The mineralogy and composition of the kaolin minerals and the development of the various morphological forms of halloysite and kaolinite in different parts of the profiles are attributed to the chemistry of the ambient solutions. However, other physical and microenvironmental conditions (e.g. time and space available) also seem to have strong influence on the precipitation processes producing the morphological variations.

Two soil sequences in northern Italy (Val di Fiemme and Val Genova) along an elevational gradient ranging from moderate (950 m a.s.l.) to high alpine (2440 m a.s.l.) climate zones were investigated with respect to element losses (Ca, Mg, K, Na, Fe, Al, Si, Mn) and development of clay minerals. Soils formed on paleo-rhyolitic parent material in Val di Fiemme and on tonalitic-granodioritic morainic material in Val Genova. All the soils have a similar age (∼12,000 y) and have been classified as Podzols. The soils are very acid and the pH values tend to increase with decreasing altitude. Podzolization processes were most intense in the range of the subalpine forest up to the timberline (1400–1900 m above sea-level (a.s.l.)). Element leaching was greatest in this range and weathering rates decrease with both higher and lower altitudes. Due to the different lithologies and precipitations between the two valleys, the total amount of chemical weathering was slightly different, although the same trends with altitude could be observed. Imogolite-type materials (ITM) are generally of minor importance. Greater concentrations of ITM were observed in the Bhs or Bs horizons of the Episkeleti-Entic Podzols at the lower altitudes. Iron eluviation was similar in all Podzols while larger amounts of eluviated Al were detected in Val Genova. The pattern of smectite distribution along the climosequences had similarities to the trend of cation losses. The largest amount of low-charge expandable minerals seems to exist in the range of the subalpine forest up to the timberline. The development of clay minerals with a smaller layer charge was more advanced in Podzols on rhyolitic material where smectite could be detected in the Bhs and Bs horizon. Parent material influenced chemical weathering in the soils along the two climosequences and essentially determined the degree of weathering and the formation of clay minerals.

The Precambrian Villa Mónica Formation clay was analyzed using petrographic and scanning electron microscopy, X-ray diffraction and chemical analysis, with the aim of characterizing the Ti-bearing phases present and determining their possible origin and/or source. Two Ti-bearing minerals were found to be present, rutile and anatase. The crystals are needles between 5 and 15 µm in size, with no evidence of abrasion or corrosion. They are commonly found in association with the (001) faces of illite flakes or in the pores between the flakes. Their disposition is similar in the three quarries studied. No zonation or differential settling due to differences in specific gravity was observed. In addition, chemical analyses indicated a positive correlation between TiO2 and K2O suggesting that both oxides behave similarly after the deposition of the sediment. The TiO2 content in the bulk fraction ranges from 0.8 to 1.98 wt.%, values that are similar to those exhibited in other clay deposits from different ages and geneses.

All observations are consistent with an in situ origin of these Ti-bearing phases during post-depositional processes that included recrystallization of existing minerals and crystallization of new phases. The original detrital minerals such as biotite, ilmenite as well as detrital illite, were the primary sources of the TiO2 and of the Fe oxides that coat the clay. Understanding the origin and the reaction mechanisms involved during the post-depositional alteration of the Villa Mónica Formation suggests that the Ti-bearing phases in different sediment types were formed by similar mechanisms involving redox processes at low to medium temperatures, even in Precambrian sediments where the presence of rutile could lead to an incorrect assumption of high temperatures involved.

Compositional data for 464 clay minerals (2:1 type) were analyzed by statistical techniques. The objective was to understand the similarities and differences between the groups and subgroups and to evaluate statistically clay mineral classification in terms of chemical parameters. The statistical properties of the distributions of total layer charge (TLC), K, VIAl, VIMg, octahedral charge (OC) and tetrahedral charge (TC) were initially evaluated. Critical-difference (P = 1%) comparisons of individual characteristics show that all the clay micas (illite, glauconite and celadonite) differ significantly from all the smectites (montmorillonite, beidellite, nontronite and saponite) only in their TLC and K levels; they cannot be distinguished by their VIAl, VIMg, TC or OC values which reveal no significant differences between several minerals.

Linear discriminant analysis using equal prior was therefore performed to analyze the combined effect of all the chemical parameters. Using six parameters [TLC, K, VIAl, VIMg, TC and OC], eight minerals groups could be derived, corresponding to the three clay micas, four smectites (mentioned above) and vermiculite. The fit between predicted and experimental values was 88.1%. Discriminant analysis using two parameters (TLC and K) resulted in classification into three broad groups corresponding to the clay micas, smectites and vermiculites (87.7% fit). Further analysis using the remaining four parameters resulted in subgroup-level classification with an 85–95% fit between predicted and experimental results. The three analyses yielded D2 Mahalanobis distances, which quantify chemical similarities and differences between the broad groups, within members of a subgroup and also between the subgroups. Classification functions derived here can be used as an aid for classification of 2:1 minerals.

Due to the importance of clay minerals in metal sorption, many studies have attempted to derive mechanistic models that describe adsorption processes. These models often include several different types of adsorption sites, including permanent charge sites and silanol and aluminol functional groups on the edges of clay minerals. To provide a basis for development of adsorption models it is critical that molecular-level studies be done to characterize sorption processes. In this study we conducted X-ray absorption fine structure (XAFS) and electron paramagnetic resonance (EPR) spectroscopic experiments on copper (II) sorbed on smectite clays using suspension pH and ionic strength as variables. At low ionic strength, results suggest that Cu is sorbing in the interlayers and maintains its hydration sphere. At high ionic strength, Cu atoms are excluded from the interlayer and sorb primarily on the silanol and aluminol functional groups of the montmorillonite or beidellite structures. Interpretation of the XAFS and EPR spectroscopy results provides evidence that multinuclear complexes are forming. Fitting of extended X-ray absorption fine structure spectra revealed that the Cu-Cu atoms in the multinuclear complexes are 2.65 Å apart, and have coordination numbers near one. This structural information suggests that small Cu dimers are sorbing on the surface. These complexes are consistent with observed sorption on mica and amorphous silicon dioxide, yet are inconsistent with previous spectroscopic results for Cu sorption on montmorillonite. The results reported in this paper provide mechanistic data that will be valuable for modeling surface interactions of Cu with clay minerals, and predicting the geochemical cycling of Cu in the environment.

The adsorption of poly(vinyl alcohol) (PVA) on montmorillonites saturated with calcium (Ca-Mt) and sodium (Na-Mt) as a function of the pH value and PVA concentration in aqueous solution was studied. Owing to the binding effect of the bivalent cation, the adsorption of PVA on Ca-Mt decreases as the pH of the suspension increases, whereas adsorption on Na-Mt is unaffected by the suspension pH. The adsorption maximum of PVA (pH 6) on Ca-Mt was 151.2 mg of PVA g−1 of clay, which is considerably lower than that on Na-Mt (496.2 mg g−1). These adsorption data coincide with the basal spacings obtained for the clays: 1.72 and 2.26 nm for Ca-Mt and Na-Mt, respectively. Sodium permits a greater separation between the clay laminae than calcium, but in both clays the presence of the polymer gives rise to a material in which PVA is intercalated between the laminae and is also adsorbed on the external surface. Adsorption is a slow process and is irreversible in both clays.

Sorption of the herbicide isoxaflutole and its main degradate, diketonitrile (DKN), to natural clays, SAz-1, SWy-2 and SHCa-1, and the organoclay derivatives (octadecylammonium (ODA) and hexadecyltrimethylammonium (HDTMA)) of these clays was investigated. Isoxaflutole hydrolysis to DKN was too rapid in aqueous solutions with organoclays to characterize sorption. No measurable DKN sorption was observed for the natural clays. Sorption of DKN was greater on organoclays with an interlayer paraffin-like complex that were prepared from the high-charge SAz-1 clay than on organoclays with a bilayer or monolayer interlayer complex prepared using lower-charge SWy-2 or SHCa-1 clays. Desorption isotherms indicated that sorption was irreversible. For SAz-1 with HDTMA at ∼100% of the clay CEC, the d001 values suggest that DKN enters the interlamellar space of the organoclay and dissociates into the anion. The DKN anion forms a very stable chelate complex with the residual cations and/or partially-coordinated structural cations. This strong interaction supports the irreversibility of the sorptive process.

The ordering conformation of surfactant molecules in intercalated montmorillonite prepared at various concentrations was investigated by 13C MAS NMR. The 13C MAS NMR study demonstrates the coexistence of ordered and disordered chain conformations. Two main resonance peaks are associated with the backbone alkyl chains: the resonance at 33 ppm corresponds to the ordered conformation (all-trans), and the resonance at 30 ppm corresponds to the disordered conformation (mixture of trans and gauche). Deconvolution of 13C MAS NMR spectra indicates that the ordering conformation of surfactant molecules within the gallery of montmorillonite depends very much on their orientation and packing density. When amine chains are oriented parallel to the silicate layers, the amount of all-trans conformer decreases with the increase of amine concentration. However, the amount of all-trans conformer increases with the increase of amine concentration when amine chains radiate from the silicate layers. Furthermore, 13C MAS NMR spectra show that the intercalated surfactant molecules in the clay minerals never attained the complete liquidlike or solidlike behavior.

The order-disorder behavior of the isomorphous cation substitution of the octahedral sheet of phyllosilicates was investigated by Monte Carlo simulations based only on atomistic models in some three-species systems Al/Fe/Mg including a wide range of different octahedral compositions that can be relevant to clay compositions found in nature, especially for smectites and illites. In many cases, phase transitions do not occur, in that long-range order is not attained, but most systems exhibit short-range order at low temperature. The ordering of the octahedral cations is highly dependent on the cation composition. Variations in the tetrahedral charge (smectite vs. illite) produce slight differences in the cation distribution and the short-range and long-range order of octahedral cations do not change drastically. The average size of Fe clusters and the long-range order of Fe are not larger in illites than in smectites as previous reports concluded, but the proportion of Fe3+ cations non-clustered is higher in smectites than in illites. This behavior supports the experimental behavior of the Fe effect on the Al-NMR signal, which is lower in illites than in smectites.

Cesium uptake by plants depends on adsorption/desorption reactions in the soil, as well as root uptake processes controlled by the plant. In this study, sorption and desorption of Cs+ on reference illite (IMt-1) was investigated in the presence of oxalate to gain understanding of mechanisms by which plant root exudates may influence Cs+ bioavailability in micaceous soils. Cesium sorption on illite decreased significantly as oxalate concentration increased from 0.4 to 2 mM. Cesium desorption from illite increased significantly with increasing oxalate concentration. Desorption of Cs+ by exchange with Na+, Ca2+ and Mg2+ was significantly enhanced in the presence of oxalate as selectivity for Cs+ decreased with respect to these ions in the presence of oxalate. On the other hand, oxalate had little effect on the Cs+/K+ selectivity coefficient. This suggests that oxalate treatments increase the relative proportion of exchange sites that are not highly selective for Cs+ and K+; e.g. ‘planar’ sites. The results indicate that oxalate plays an important role in Cs+ binding on illite and, therefore, plant rhizosphere chemistry is likely to alter Cs+ bioavailability in micaceous soils.

Fe(II)–Fe(III) green rust identified in soil as a natural mineral is responsible for the blue-green color of gley horizons, and exerts the main control on Fe dynamics. A previous EXAFS study of the structure of the mineral confirmed that the mineral belongs to the group of green rusts (GR), but showed that there is a partial substitution of Fe(II) by Mg(II), which leads to the general formula of the mineral: ${[{\text{Fe}}_{1-x}^{2+}{\text{Fe}}_x^{3+}{\text{Mg}}_y{(\text{OH})}_{2+2y}]}^{x+}{[x{\text{OH}}^{-}\cdot m{\text{H}}_2\text{O}]}^{x-}$${[{\rm{Fe}}_{1 - x}^{2 + }{\rm{Fe}}_x^{3 + }{\rm{M}}{{\rm{g}}_y}{({\rm{OH}})_{2 + 2y}}]^{x + }}{[x{\rm{O}}{{\rm{H}}^ - } \cdot m{{\rm{H}}_2}{\rm{O}}]^{x - }}$. The regular binary solid-solution model proposed previously must be extended to ternary, with provision for incorporation of Mg in the mineral. Assuming ideal substitution between Mg(II) and Fe(II), the chemical potential of any Fe(II)-Fe(III)-Mg(II) hydroxy-hydroxide is obtained as: $\text{μ}=X_1{\text{μ}}_{\text{1}}^{\text{o}}+X_2{\text{μ}}_{\text{2}}^{\text{o}}+X_3{\text{μ}}_{\text{3}}^{\text{o}}+\text{R}T[X_1\text{ln}{X}_1+X_2\text{ln}{X}_2+X_3\text{ln}{X}_3]+A_{12}{X}_2(1-X_2)$${\rm{\mu }} = {X_1}{\rm{\mu }}_{\rm{1}}^{\rm{o}} + {X_2}{\rm{\mu }}_{\rm{2}}^{\rm{o}} + {X_3}{\rm{\mu }}_{\rm{3}}^{\rm{o}} + {\rm{R}}T[{X_1}{\rm{ln}}{X_1} + {X_2}{\rm{ln}}{X_2} + {X_3}{\rm{ln}}{X_3}] + {A_{12}}{X_2}(1 - {X_2})$. All experimental data show that the mole ratio X2 = Fe(III)/[Fetotal + Mg] is constrained (1) structurally and (2) geochemically. Structurally, Fe(III) ions cannot neighbor each other, which leads to the inequality $X_2\alpha \raisebox{1ex}{$1$}\!\left/ \!\raisebox{-1ex}{$3$}\right..$${X_2}\leqslant {\raise0.5ex\hbox{$\scriptstyle 1$}\kern-0.1em/\kern-0.15em\lower0.25ex\hbox{$\scriptstyle 3$}}.$ Geochemically, Fe(III) cannot be too remote from each other for GR to form as Fe(OH)2 and Mg(OH)2 are very soluble, so $X_2\alpha \raisebox{1ex}{$1$}\!\left/ \!\raisebox{-1ex}{$4$}\right.$${X_2}\geqslant {\raise0.5ex\hbox{$\scriptstyle 1$}\kern-0.1em/\kern-0.15em\lower0.25ex\hbox{$\scriptstyle 4$}}$. A linear relationship is obtained between the Gibbs free energy of formation of GR, normalized to one Fe atom, and the electronegativity ϰ of the interlayer anion, as: μo/n = −76.887ϰ — 491.5206 (r2 = 0.9985, N = 4), from which the chemical potential of the mineral fougerite μ is obtained in the limiting case X3 = 0, and knowing ${\text{μ}}_{\text{1}}^{\text{o}}=-489.8$${\rm{\mu }}_{\rm{1}}^{\rm{o}} = - 489.8$ kJmol−1 for Fe(OH)2, and ${\text{μ}}_{\text{3}}^{\text{o}}=-832.16$${\rm{\mu }}_{\rm{3}}^{\rm{o}} = - 832.16$ kJmol−1 for Mg(OH)2, the two unknown thermodynamic parameters of the solid-solution model are determined as

${\text{μ}}_{\text{2}}^{\text{o}}=+119.18{\text{kJmol}}^{-1}$${\rm{\mu }}_{\rm{2}}^{\rm{o}} = + 119.18\;{\rm{kJmo}}{{\rm{l}}^{ - 1}}$ for Fe(OH)3 (virtual), and A12 = −1456.28 kJmol−1 (non-ideality parameter). From Mössbauer in situ measurements and our model, the chemical composition of the GR mineral is constrained into a narrow range and the soil solutions-mineral equilibria computed. Soil solutions appear to be largely overstaurated with respect to the two forms observed.