In this paper atomic force microscopy-studies are reported suggesting the existence of vicinal faces on the (100) plane of artificially grown goethite. Goethite crystals are commonly regarded to have boundary planes of (100), (010) and (001) faces. In contradiction to these theoretical models TEM and SEM images exhibit (110) and (021) faces to be dominating. These goethite particles consist of many crystallographic coherent domains so that the existence of dislocations on the surfaces has to be assumed. These sites on the surfaces may serve as a nucleation site for the formation of steps. The vicinal faces on the (100) face found with the AFM are (021) faces. They influence the growth velocity of the (100) face to such a degree, that this face vanishes and only (110) faces remain as stable boundary surfaces. The (021) faces are also stable, but have the highest growth rate among the faces considered.

Redox properties of iron-bearing mineral surfaces may play an important role in controlling the transport and transformation of pollutants into ground waters. Suspensions of seven iron-bearing minerals were reacted with pH and redox indicators under anaerobic conditions at the pH of the natural suspension. The responses of the indicators to the mineral surfaces were monitored by UV-visible spectroscopy using a scattered transmission technique. The Hammett surface acidity function (Hs) and the surface redox potential (Ehs) of these iron-bearing minerals were measured. These measured values were used to calculate Eh values for the seven minerals: goethite = +293 mV; chlorite = +290 mV; hematite = +290 mV; almandite = +282 mV; ferruginous smectite = +275 mV; pyrite = +235 mV; and Na-vermiculite = +223 mV. Calculated surface redox potentials of minerals are different from their potentials measured by platinum electrode in bulk suspensions. UV-visible spectroscopy provides a quick and non-destructive way of monitoring organic probe response at the mineral surface.

Layer stackings in the ideal and real kaolinite structures are considered in terms of layer orientations i = 1, 2, … 6, intra- and interlayer displacements of adjacent 0- and T-sheets, si and tk, distortions of these displacements δ1 and δ2, deviations of unit cell parameters ηi = b2i/a2i − 3, εi = γi − π/2, and normal projections cn of the axis vector c on the ab plane.

The ideal monoclinic angle of dickite (cnx = −1/3) and the deviation α - π/2 ≠ 0 for kaolinite are explained by combinations of the δ1 and δ2 values in the sequence of symbols si and tk defining the corresponding structures. Twenty stacking variants in the 3 successive layers of the kaolinite structure are derived, incorporating layer orientations of the same parity, displacements t+, − = [0, ± 1/3] and reflection operations in planes normal to the axis b3. Two deformation mechanisms are proposed for the accommodation of successive layer unit cells adjusting either angular or linear parameters at the agreement of either linear or angular parameters corresponding.

Various size fractions of several samples of glauconitic clay and illite were heated stepwise under vacuum for extended periods to: 1) evaluate radiogenic-argon (Ar) yields in relation to composition and size range; and 2) investigate the kinetics of radiogenic-Ar release. Each sample was heated at 250, 375, 500 and 1000 °C.

The radiogenic-Ar release patterns are nearly the same for the various size fractions of each sample. The Ar yields are not functions of particle size, at least not in these size ranges. This observation suggests that the kinetics of radiogenic-Ar release from these materials under these experimental conditions may be controlled by some mechanism other than diffusion.

The experiments show distinct differences in yield of radiogenic Ar from glauconitic clay and illite, which were most evident in the 375 and 500 °C steps. The yield (relative to the total amount of radiogenic Ar in the sample) at a particular temperature is inversely related to potassium (K) content, and there appears to be a direct dependence of yield on the iron (Fe) content. Because the literature provides evidence that Ar release during heating of phyllosilicates under vacuum is controlled by dehydroxylation and also provides evidence that dehydroxylation of clay may follow first-order kinetics, the kinetic data on Ar release from these samples were compared to simulated first-order reactions. To match the obser- vational data requires more than 2 activation energies in each simulation, which is consistent with the known mineralogical heterogeneity of such samples.

Progressively buried sandstones and shales of the Mahakam Delta Basin in Indonesia were studied. Mineralogical, morphological and K-Ar isotopic data were obtained for clay, mica and feldspar minerals. The data indicate that K necessary for the illitization of illite/smectite mixed-layer minerals was supplied mainly from K-feldspar alteration within the sandstones and from mica within the shales. Most of the K-feldspar alteration for both the shale and sandstone samples were observed outside the main zone of illitization, which is restricted to the upper 2000 m of sediment. The feldspar grains were altered below this depth for both lithologies. Therefore, illitization requires an open sedimentary system. This is in contrast to the illitization model for deeply buried shales of the Gulf Coast. That system is commonly assumed to be a closed K system.

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 grey-green peloids from the Miocene period to Recent fine-grained deposits on the continental shelf close to Congo-Zaîire River mouth were studied by X-ray transmission diffractometry (XRD), SEM and by EDAX. The peloids have multiphase heterogenous mineral composition. Their most important constituents are detrital minerals like kaolinite, quartz, goethite, 7 Å phases with d(001) ≈ 7.3 Å, and in more maturated grains—nontronite. The d(060) values were used to estimate the general composition of phyllosilicate phases to compare with the composition determined by EDAX. It has been found that d(060) equal to 1.504 Å is common for Fe3+-bearing kaolinite, which is quite abundant for the Recent peloids. The d(060) equal to 1.535 Å and 1.55 Å is characteristic for the di-trioctahedral and trioctahedral 1:l phases, which are abundant within the more evolved Miocene peloids. Nontronite is characterized by d(060) equal to 1.524 Å within concordance with its highly ferrous composition, and partly by its potassic interlayer. It shows cabbage-like nannostructures proving neoformational origin of this mineral in the marine environment.

It has been shown that areas of the low sedimentation rate within the Congo Basin were favorable for the mineral changes and neoformation. For the Holocene vertical profile, we observed levels of slower sedimentation rates. The evolution is expressed by the disappearance of kaolinite at the expense of other 7 Å phases and nontronite. Although more advanced stages of maturation of the studied phases were observed in older peloids (104 to 107 y), one cannot detect a linear relationship of these processes with burial.

Prograde evolution of illite/smectite occurring in an unusually-thick (8000 m) sequence of Mesozoic-Cenozoic sediments in the Basque-Cantabrian Basin, Spain, has been studied using XRD and TEM/AEM. The sediments, which are only slightly tilted, cover the range from smectite to illite, and the most deeply buried ones are unique in that they span the range from diagenesis through low-grade metamorphism (anchizone), with no apparent overprinting due to tectonic deformation.

Pelites are absent from the shallow section, but smectite occurs in marls as high-charge, K-dominant and low-charge, K-poor anastomosing arrays of layers. At intermediate depths, authigenic clay is identified largely as R1 I/S, coexisting with packets of R≫3 I/S (nearly pure illite), where illite-like and smectitelike layers can be identified by contrast in TEM images, which is consistent with XRD data. The authigenic clay of the deepest samples consists of illite with no or almost no expandable layers, which occurred as packets with layers largely subparallel to bedding, K-deficient composition in comparison with muscovite, 1Md-like SAED patterns, and 100 Å mean packet thickness. There is no evidence of deformation stress-induced, non-bedding-parallel clays in the deepest samples. Detrital micas with either a phengiterich or a phengite-poor composition range dominate the phyllosilicate fraction of all the samples. Detrital micas show no changes over the diagenesis/metamorphism range and appear to have behaved as if isolated from authigenic clays.

Authigenic clays occur as bedding-subparallel packets that evolved during passive burial metamorphism through dissolution/crystallization of less-evolved clays. Where illite-like and smectite-like layers can be identified, TEM images imply a discontinuous series in which packets of R1 I/S (50% I) transform to packets of nearly-pure illite, that is, an Ostwald-step-rule-like sequence. Such immature illite remains unmodified with further burial, and is apparently the potential predecessor of stress-induced, highly-evolved mica of higher-grade, tectonically-deformed pelites.

The upper 15−20 m of a 200 m thick lateritic weathering profile on Precambrian itabirites of Capanema, Brazil, reveals a genetic pathway for the formation of hematitic and goethitic nodules in the ferruginous crust through a very fine grain Al-hematite and Al-goethite mixture, called here the brick-red-material (brm). This evolution develops between the soft saprolite and a 10 m thick indurated ferruginous crust. The soft saprolite retains the original structures of the itabirite and is characterized by almost complete dissolution of quartz, the development of goethite septa, and the partial dissolution of primary hematite. Near the contact with the overlying ferruginous crust, the brm is gradually filling voids as well as replacing primary hematite and goethite in the saprolite. In the upper indurated crust, the brm transforms into coarse structureless ferruginous nodules (aluminous hematites and goethites) and is the precursor of the hematito-goethitic nodules of the crusts. Crystallization of newly-formed Al-goethite and Al-hematite within the brm occurs without detectable amounts of amorphous iron oxides of ferrihydrite precursors.

The present paper represents an extension of recent work that considered the partitioning response of binary solvents placed into contact with charged, expandable clays. Previous theoretical work yielded a model of partitioning by performing a thermodynamic analysis, involving the work of polarization, on a binary solvent, treated as a continuum and residing within the interlayer space of a layered aluminosilicate clay. Partitioning, or the tendency for sorbed and bulk phases to have different compositions, was shown to be sensitive to the dielectric properties of the 2 solvents of the binary mixture and to the surface charge density on the clay, among other factors. Although previous experimental work has helped to validate the theory, additional work is reported here that looks at hysteresis effects, the role of the exchangeable cation (usually organic), the prediction of adsorption isotherms and the contribution that partitioning, or sorption, makes to the disjoining pressure that develops in binary solvent systems. In this current study, 3 different organo-clays were considered: Cetyltrimethylammonium (CTMA), Isopropanolammonium (IPA), and Benzylammonium (BA) montmorillonite. Solvent systems under study included: acetone/chloroform (a-c), acetone/quadricyclane (a-q) and acetonitrile/chloroform (an-c). While partitioning of the a-c system on CTMA-clay follows theory quite well, theory tends to over-predict partitioning for the a-q system on the same clay and under-predict partitioning for the an-c system on all clays. Predicted adsorption isotherms range from highly nonlinear to nearly linear. Finally, the delamination and subsequent swelling processes of BA-clay in a water/acetonitrile binary solvent system are very sensitive to composition, a result that is directly linked to the partitioning process.

The compositions, fabrics and structures of authigenic minerals that formed recently from silicic volcanic ash layers from a 1300-meter sediment column obtained at ODP Site 808 of the Nankai Trough were studied using XRD, STEM, AEM and SEM. Smectite and zeolites were first detected as alteration products of volcanic glass with increasing depth, as follows: smectite at 200 m below seafloor (mbsf) (20 °C), clinoptilolite at 640 mbsf (60 °C) and analcime at 810 mbsf (75 °C).

A primitive clay precursor to smectite was observed as a direct alteration product of glass at 366 mbsf (approximately 30 °C). High defect smectite with lattice fringe spacings of 12 to 17 Å and having a cellular texture filling pore space between altering glass shards occurs at 630 mbsf. Packets of smectite become larger and less disordered with increasing depth and temperature. The smectite that forms as a direct alteration product of volcanic glass has K as the dominant interlayer cation.

With increasing depth, smectite becomes depleted in K as the proportion of clinoptilolite increases, and then becomes depleted in Na as the proportion of analcime increases. The composition of the exchangeable interlayer of smectite appears to be controlled by the formation first of K-rich clinoptilolite and then Na-rich analcime, via the pore fluid, giving rise at depth to Ca-rich smectite. Smectite reacted to form illite in the interbedded shales but not in the bentonites. Paucity of K in smectite and pore fluids, due to formation of clinoptilolite under closed system conditions, is believed to have inhibited the reaction relative to shales.

Complexes formed between montmorillonite, saturated in Li+, Na+, Mg2+, Ca2+, Co2+, Fe3+, Cu2+ and Zn2+, and trimethyl phosphites (TMP) and triethyl phosphites (TEP) were studied. In all of the cases, phosphites penetrate into the interlayer space of the montmorillonite and produce solvates whose basal spacing varies depending on the characteristics of the exchangeable cation. All the complexes with low basal spacing (Li+, Na+, Mg2+, Co2+ and Zn2+) are stable in vacuum, whereas those with high basal spacing, formed by the Ca2+ sample with TMP, and Ca2+ and Fe3+ samples with TEP are transformed into low basal spacing complexes in vacuum. The complexes with high basal spacing (Cu2+ sample with TMP and TEP) are stable in vacuum.

The TMP and TEP complexes stable in vacuum with low spacing are thermally destroyed in one or two stages with two loss maxima, as a result of partial burning of phosphite molecules. Those with high spacing (Cu2+) are destroyed in two stages; the first is probably the result of the transformation process from high to low spacing, as a consequence of the structural reorganization of the molecules which remain in the interlayer space, and the second, could be associated with the destruction of low spacing complexes.

The IR spectra show that the molecule and the cation are linked by the P of the phosphite, which produces a reinforcement of the other bonds in the molecule, caused by an inductive effect. The phosphite intercalation is accompanied by a partial isomerization of phosphite to phosphonate.

The heat of adsorption of phosphites shows that the molecule-cation bond is ion-dipole. In the Cu sample with trimethyl phosphite, this bond seems to be reinforced by retrodonation of electrons from copper to ligand. Finally, the possible disposition of phosphite molecules in the interlayer space is considered. For this purpose, ab initio calculations have been performed on the different conformers of the TMP molecule at 6–31G* and 6–31+G* basis sets.

Structural transformations of illite-smectite samples of hydrothermal genesis with increasing contents of illite layers were studied by X-ray powder diffraction. The samples were K-saturated and subjected to wetting and drying cycles to increase three-dimensional structural ordering. Diffraction profiles were analyzed with the help of a specially devised computer program based on the approximation of individual diffraction reflections by “bell-shaped” functions, with minimization of the differences between experimental and simulated profiles. The data indicate that the transformations of these illite-smectite samples were accompanied not only by variations in the proportion of illite and smectite layers and in the pattern of their alternation, but also by a change in structure within 2:1 layers.

The changes in amount and location of layer charge during diagenetic alteration have been investigated for smectites and smectite layers of illite/smectite interstratified minerals (I/S) by X-ray powder diffraction analysis with various expansion behavior tests: 1) ethylene glycol (EG) solvation (XRD); 2) K-saturation and EG solvation; 3) Li-saturation, heating at 250 °C and glycerol or EG solvation (Greene-Kelly test); and 4) alkylammonium saturation. In the course of low-temperature diagenesis but before the onset of illitization, mean layer charge of smectites continuously increases from approximately 0.56 to 0.73 per O20(OH)4 with increasing depth, and tetrahedral charge also increases continuously from approximately 0.21 to 0.38 per O20(OH)4 (beidellitization). The continuous increase in tetrahedral charge without change in peak intensity and shape suggests that the solid-state Al for Si substitution mechanism appears to predominate within beidellitization. After illitization, the content of the beidellitic layers continuously decreases, while the mean layer charge of expandable layers and the content of illite layers in I/S increase. This suggests that the conversion of a beidellitic layer to an illitic layer preferably occurs during early illitization. Thus, before illitization, beidellite-like layers are formed from precursor smectite, and during the early stage of illitization, the high charged beidellitic layers are probably consumed to form illite layers.

Sedimentary zeolites clinoptilolite, mordenite and erionite occur as diagenetic products of ash falls of rhyolitic composition from the Oligocene Chichindaro Formation at the limits of the Mexican Volcanic Belt with the Mexican Highland. These zeolitic tuffs were formed from open hydrologic environments where rhyolitic glass altered to clinoptilolite + opal-C and to clinoptilolite + mordenite + erionite + opal-C. The process of diagenesis was hydrolysis associated with the removal of SiO2, K2O, and Na2O from the rhyolitic precursor and enrichment of Al2O3, MgO, and CaO. The crystallization of clinoptilolite occurs at ratios of SiO2/Al2O3 between 4.91 and 7.14 and (K2O + Na2O)/(MgO + CaO) from 2.19 to 0.79. Formation of clinoptilolite appears to be directly from glass and through a vitreous proto-zeolite intermediate. The zeolitic tuff is in contact with a vitric tuff where ash falls were devitrified to K-feldspar and diagenetically altered to smectite + opal-C.

Diffuse Reflectance Fourier Transform Infrared spectroscopy was used to monitor both molecular interactions and concentrations of volatile organic chemicals adsorbed on a commercial montmorillonite. Chemicals tested included propanoic acid, hexanal, heptanal, trimethylamine, dimethylsulfide and dimethyldisulfide. Diffuse Reflectance Fourier Transform Infrared spectroscopy had several advantages over other infrared techniques including ease of sample preparation, greater numbers of useful bands and the ability to detect both major and minor components from the same spectra. Evidence for the formation of organo-clay complexes was found for all chemicals except dimethylsulfide. Spectra of mixed chemicals on the clay showed numerous overlapping bands. Organic concentrations were determined by multicomponent analysis using a least squares curve fitting technique. Significant correlation (P < 0.01) between actual and determined concentrations of added organics was obtained for all except dimethylsulfide. Here the weak spectral contribution appeared to be overshadowed by the strongly adsorbing montmorillonite with consequent decrease in sensitivity. Diffuse Reflectance Fourier Transform Infrared spectroscopy of organo-montmorillonite complexes could be used both as a means of studying molecular interactions and for the determination of adsorbed organic concentrations.

Redox and acid-base reactions play important roles in the fate of metal contaminants in soils and sediments. The presence of significant amounts of Cr, Pb and other toxic heavy metals in contaminated soils and sediments is of great environmental concern. Oxidation states and dissolution characteristics of the heavy metals can exert negative effects on the natural environment. Atomic force microscopy (AFM) was used to follow the changes in morphology and structure of reaction products of Cr and Pb formed on mineral surfaces. Nitrate salts of Cr(III) and Pb(II) were used to replace the native exchangeable cations on muscovite and smectite surfaces and the metal-mineral systems were then reacted at different pH's and redox conditions.

For Pb, aggregate morphological forms were found at pH 6.1 and 12.4. At pH 6.1, the mean roughness value was 0.70 nm, and at pH 12.4 it was 5.30 nm. The fractal dimensions were 2.03 at pH 6.1 and 2.05 at pH 12.4. For Cr(III), both layered and aggregate morphological forms were found at pH 6.8 and 10.8. The mean roughness values were 0.90 nm at pH 6.8 and 4.3 nm at pH 10.8. Fractal dimensions for both were 2.00. The effect of redox conditions on morphological characteristics was studied on a smectite substrate. The reduced clays were more compacted than oxidized ones and the reduced clay could reduce Cr(VI) to Cr(III), forming new minerals on the surfaces.

A geochemical equilibrium model, MINTEQA2, was used to simulate the experimental conditions and predict possible reaction products. Simulation results agreed well with data from experiments, providing evidence that modeling can provide a useful “reality check” for such studies. Together, MINTEQA2 and AFM can provide important information for evaluating the morphologies and chemical reactivities of metal reaction products formed on phyllosilicate surfaces under varying environmental conditions.

In the 12 km2 catchment area of Syv creek, Denmark, moderate to high concentrations of nitrate (NO3−) occurred in the upper part of the oxidized zone (oxic-I), but dropped within the lower suboxic part (oxic-II), to below the detection limit in the unoxidized zone. Structural Fe2+ in the clay minerals made up 10 to 12% of the Fe in the oxidized zone and increased to approximately 50% in the unoxidized zone. Concurrent with changes in the distribution of structural Fe2+ the clay mineral constituents changed. Vermiculite was typically found in the oxidized zone whereas chlorite was found in the unoxidized zone only. A conversion of illite and chlorite into vermiculite seems to take place. A significant correlation between NO3− and the amount of reduced Fe2+ in the suboxic (oxic-II) zone, indicates that primary structural Fe2+ in the clay minerals is the reductant in a NO3− reduction process.

This investigation was carried out to study the effect of different concentrations of citric acid and glycine, which are common in freshwaters, on the kinetics of the adsorption of Hg by kaolinite under various pH conditions. The data indicate that Hg adsorption by kaolinite at different concentrations of citric acid and glycine obeyed multiple first order kinetics. In the absence of the organic acids, the rate constants of the initial fast process were 46 to 75 times faster than those of the slow adsorption process in the pH range of 4.00 to 8.00. Citric acid had a significant retarding effect on both the fast and slow adsorption process at pHs of 6.0 and 8.0. It had a significant promoting effect on the fast and slow adsorption process at pH 4.00. Glycine had a pronounced enhancing effect on the rate of Hg adsorption by kaolinite during the fast process. The rise in pH of the system further increased the effect of glycine on Hg adsorption. The magnitude of the retarding/promoting effect upon the rate of Hg adsorption was evidently dependent upon the pH, structure and functionality of organic acids, and molar ratio of the organic acid/Hg. The data obtained suggest that low-molecular-weight organic acids merit close attention in studying the kinetics and mechanisms of the binding of Hg by sediment particulates and the subsequent food chain contamination.

The adsorption of arsenate (As(V)) on kaolinite, montmorillonite and illite was investigated at varying pH and competing anion concentration while holding As(V) concentration (6.7 × 10−7M), clay suspension density (2.5 g L−1) and ionic strength (0.1 M NaCl) constant. The effects of 2 concentrations of phosphate (P) or molybdate (Mo) (6.7 × 10−7 and 6.7 × 10−6M) on As(V) adsorption envelopes (adsorption vs. pH) gave evidence for direct competitive adsorption (in the case of As(V) + P) and possibly site-specific non-competitive adsorption (As(V) + Mo). Distinct As(V) adsorption maxima occurred at approximately pH 5.0 for kaolinite, 6.0 for montmorillonite and 6.5 for illite, and ranged from 0.15 to 0.22 mmol As(V) kg−1. When both As(V) and P were present at equimolar concentrations (6.7 × 10−7M), As(V) adsorption decreased slightly, whereas As(V) adsorption substantially decreased in binary As(V)/P systems when the P concentration was 6.7 × 10−6M, which was 10 times greater than As(V). The presence of Mo at equimolar (6.7 × 10−7 M) and 10 times greater (6.7 × 10−6M) concentrations than As(V) caused only slight decreases in As(V) adsorption because the Mo adsorption maximum occurred at pH < 4. The constant capacitance surface complexation model was applied to As(V) and P adsorption data and was used to predict As(V) adsorption at varying P concentrations. The model gave reasonable descriptions of As(V) adsorption on the 3 clay minerals at varying pH and in the presence of a competing oxyanion (P), indicating that surface complexation modeling may be useful in predicting As(V) adsorption in soils.