Retention studies of the cobalt-goethite system were carried out using synthetic, star-shaped and lath-shaped pure, Al-, Cd-, Cu- and Si-associated goethites. Aluminium and Si are commonly occurring foreign elements in natural goethites. The goethites were prepared by coprecipitating Fe and the foreign element under controlled conditions and characterized by X-ray diffraction, transmission electron microscopy, specific surface area determination and 2 M HCl extraction. The foreign-element associated goethites contained ∼3, ∼5 and ∼9 mole % Al, ∼4 mole % Cd and ∼3 mole % Cu incorporated by isomorphous substitution but only ∼0.4 mole % of probably occluded Si. Crystal size and shape but also number of defects and domains, and hence specific surface area, unit-cell dimensions and reactivity towards 2 M HCl, exhibited great variability among the goethites. Accordingly the amounts of Co sorbed from initially 10−7 M Co in 0.1 M Ca(NO3)2 in relation to pH (3–8) and reaction time (2–504 h) were very different for the eight goethites. The affinity of Co is highest for Cd- and lowest for Cu-goethite. These samples also form the extremes regarding time-dependent sorption with Cu-goethite showing the smallest and Cd-goethite the largest increase in sorption with increasing reaction time. The Co uptake was not caused by precipitation Co(III) oxides due to Co(II) oxidation, since oxygen exclusion during sorption had no effect on the amount of Co sorbed. The amounts of sorbed Co extracted by 2 M HCl decreased with increasing sorption time but 40–87% of sorbed Co remained unextracted after 48 h, most in Cu-goethite and least in lath-shaped pure goethite. The strong retention suggests Co uptake by diffusion into micropores and fissures resulting from structural defects and intergrowths. The diffusion coefficients range from 3·10−19 to 6·10−17 cm2/s with the highest values for Al- and Si-associated goethites emphasizing the importance for Co immobilization, and hence availability, of foreign-element associations in goethite.

Helvetic sediments from the northern margin of the Alps in eastern Switzerland were studied by clay mineralogical methods. Based on illite “crystallinity” (Kübier index), the study area is divided into diagenetic zone, anchizone and epizone. Data on the regional distribution of the following index minerals are presented: smectite, kaolinite/smectite mixed-layer phase, kaolinite, pyrophyllite, paragonite, chloritoid, glauconite and stilpnomelane. Isograds for kaolinite/pyrophyllite and glauconite/stilpnomelane are consistent with illite “crystallinity” zones. Using the ordering of mixed-layer illite/smectite, the diagenetic zone is subdivided into three zones. The illite domain size distribution was analyzed using the Warren-Averbach technique. The average illite domain size does not change much within the diagenetic zone, but shows a large increase within the anchizone and epizone. The average illite b0 value indicates conditions of an intermediate-pressure facies series.

The Helvetic nappes show a general increase in diagenetic/metamorphic grade from north to south, and within the Helvetic nappe pile, grade increases from tectonically higher to lower units. However, a discontinuous inverse diagenetic/metamorphic zonation was observed along the Glarus thrust, indicating 5–10 km of offset after metamorphism. In the study area, incipient metamorphism was a late syn- to post-nappe-forming event.

The oxidation state of structural iron greatly influences the physical-chemical properties of clay minerals, a phenomenon that may have significant implications for pollutant fate in the environment, for agricultural productivity, and for industrial uses of clays. Knowledge of redox mechanisms is fundamental to understanding the underlying basis for iron's effects on clays. Past studies revealed that the extent of Fe reduction varied depending on the reducing agent used, but this variation may not have been a simple function of the reduction potential of the reducing agent. The objective of this study was to identify the relationship between the Fe reduction mechanism and free radical activity in the reducing agent. Several reducing agents and their mixtures with the Na-saturated, 0.5 to 2 μm size fraction of ferruginous smectite (SWa-1) were analyzed by electron spin resonance (ESR) spectroscopy to determine the presence of unpaired electrons or free radicals. Only Na2S2O4 exhibited paramagnetic free-radical behavior with a signal at about g = 2.011, which was attributed to the sulphoxylate (S02− ·) free radical. The free radical was labile in aqueous solution, and the ability of Na2S2O4 solution to reduce structural Fe in the smectite decreased with age of the solution and paralleled the disappearance of the free radical signal in the ESR spectrum. The paramagnetic species was preserved and enhanced if Na2S2O4 was added to the clay suspension, indicating that either the clay surface stabilized the SO2− · radical or the additional unpaired electrons were produced in the clay structure.

Kaolinite from the Black Ridge, Clermont, has relatively low δ18O (12.3‰ to 14.8‰) and very low δD values with a large variation (−120‰ to −85‰). Comparison of these data with those from the nearby Denison Trough and elsewhere in eastern Australia, together with previous studies of the mineralogy of the sedimentary rocks, suggests that extensive kaolinization of the “White Section” resulted from weathering during the Late Triassic to Early Jurassic periods. The relatively large variation in δD values of kaolinite probably derives from post-formational isotopic exchange with other fluids.

The similarity between δ18O values of kaolinites from Black Ridge and from the Denison Trough suggests that the small Miclere-Black Ridge basin may have been part of the Denison Trough before the Late-Triassic inversion. The preservation of original δD values in kaolinite at Black Ridge indicates that unlike the Denison Trough, which was reburied at more than 1000 m, the Miclere-Black Ridge basin was not rebuffed at great depth during the Mesozoic period.

The electrochemical properties of kaolinite before and after modification with chlorodimethyl-octadecylsilane have been studied by electrophoretic mobility, surface charge titration, and extrapolated yield stress measurements as a function of pH and ionic strength. A heteropolar model of kaolinite, which views the particles as having a pH-independent permanent negative charge on the basal planes and a pH-dependent charge on the edges, has been used to model the data. The zeta potential and surface charge titration experimental data have been used simultaneously to calculate acid and ion complexation equilibrium constants using a surface complex model of the oxide-solution interface. The experimental data were modeled following subtraction of the basal plane constant negative charge, describing only the edge electrical double layer properties. Extrapolated yield stress measurements along with the electrochemical data were used to determine the edge isoelectric points for both the unmodified and modified kaolinite and were found to occur at pH values of 5.25 and 6.75, respectively. Acidity and ion complexation constants were calculated for both sets of data before and after surface modification. The acidity constants, pKa1 = 5.0 and pKa2 = 6.0, calculated for unmodified kaolinite, correlate closely with acidity constants determined by oxide studies for acidic sites on alumina and silica, respectively, and were, therefore, assigned to pH-dependent specific chemical surface hydroxyl groups on the edges of kaolinite. The parameters calculated for the modified kaolinite indicate that the silane has reacted with these pH-dependent hydroxyl groups causing both a change in their acidity and a concomitant decrease in their ionization capacity. Infrared data show that the long chain hydrocarbon silane is held by strong bonding to the kaolinite surface as it remains attached after washing with cyclohexane, heating, and dispersion in an aqueous environment.

Fe(II) and Fe(III) in various proportions were coprecipitated by NH3 at pH ≈ 11. The Fe(II)/Fe(III) ratio (x) was varied from 0.10 to 0.50. After stabilization by aging at pH ≃ 8 in anaerobic conditions, hydrous precipitates were characterized by electron microscopy, Mössbauer spectroscopy, and kinetics of dissolution in acidic medium. At any x value, all stable products exhibited the structure of (oxidized) magnetite. For x ≤ 0.30, two distinct species were coexisting: the one (“m”) was made up of ca. 4nm-sized particles with a low Fe(II) content (Fe(II)/Fe(III) ≈ 0.07), and the other (“M”) consisted of particles of larger, more or less distributed sizes, and composition Fe(II)/Fe(III) ≈ 0.33; “M” increased relative amount with increasing x. For x ≥ 0.35, “M” was the only constituent and its Fe(II)/Fe(III) ratio was equal to x. “M” is identified with (nonstoichiometric) magnetite, whereas “m” is likely to be an oxyhydroxide. Mechanisms of formation are discussed, and a phase diagram is proposed which schematizes the evolution of the coprecipitation products with x and with time. Addition of Fe(II) after the precipitation of Fe(III), instead of coprecipitation, yielded very similar results.

The acidic properties of acid-modified montmorillonite and vermiculite were determined by pyridine and ammonia adsorption to correlate with the alkylating and dehydrating activity of the activated samples. Treatment of the minerals with different concentrations of hydrochloric acid results in the variation of overall acidity and density of acidic sites. Infrared (IR) spectral and differential scanning calorimetric analyses have revealed the presence of Bronsted and Lewis acid sites on the activated samples. The catalytic activity towards the above reaction has been correlated to the acid strength and density of Lewis acid sites. Treatment of montmorillonite with hydrochloric acid in the range of 0.1 and 0.3 M and vermiculite with 0.2 to 0.3 M seemed to be suitable for the conversion of methanol into olefin-rich hydrocarbons. Acid-activated montmorillonite catalyzed the isopropylation of benzene to a maximum extent of 16%, whereas acid-activated vermiculite gave a maximum conversion of only 4%.

The amount of Mn2+ adsorbed or removed from solution by birnessite is several times greater than its reported cation exchange capacity. Extractability of the sorbed Mn2+ decreases with aging. It is uncertain whether the sorbed Mn2+ is oxidized on the surface or incorporated into the structure of birnessite. Using X-ray powder diffractometry and transmission electron microscopy, a study was conducted to examine the mineralogical alteration of birnessite after treatment with various concentrations of MnSO4 and solution pH.

The sorbed Mn2+ was not directly oxidized and remained on the birnessite surface. The sorption of Mn2+ was followed by alteration of birnessite with the formation of new Mn minerals. The specific Mn minerals formed were governed by the pH of the reaction, and the rate of the transformation was determined by Mn2+ concentration and pH. Nsutite and ramsdellite were identified at pH 2.4, crypto-melane at pH 4, groutite at pH 6, and manganite at pH 8. Other Mn minerals formed at these and other pH levels could not be identified. As the concentration of Mn in the solution decreased, the time required to form new minerals from the birnessite increased. The newly formed phases were the result of structural conversion since dissolution of birnessite and reprecipitation of new phases were not observed.

The surface thermodynamic properties of a series of n-alkylammonium and quaternary ammonium treated clay films were determined by contact angle measurement of drops of test liquids using the Young equation for polar materials. The two clays were a Wyoming montmorillonite (SWy-1) and Laponite RD. For a series of primary n-alkyl (6 ≤ n ≤ 15) and several quaternary organic cations, the organo-clay (both SWy-1 and Laponite RD) showed very little change in the value of γLW compared to the equivalent ammonium-saturated clay. Also, γ⊕ remained small or increased slightly compared to the ammonium-saturated clay. For SWy-1 exchanged by both quaternary ammonium and primary n-alkylammonium cations, the value of γ⊖ was smaller (0.1 ≤ γ⊖ ≤ 15.8 mJ/m2) than for the ammonium-saturated clay (γ⊖ = 36.2 mJ/m2) and decreased linearly with the number of carbon atoms. The γ⊖ values for the organic cation-exchanged Laponite RD samples (24.2 ≤ γ⊖ ≤ 31.2 mJ/m2) were smaller than or comparable to the ammonium saturated clay (γ⊖ = 30.7 mJ/m2), and were relatively insensitive to the number of carbon atoms in the organic cation. Thus, for both clays the increased adsorption of organic molecules resulting from replacement of inorganic cations by organic cations is due primarily to the decrease in the value of the Lewis base parameter, γ⊖.

Shales have often been cited as the source of authigenic material that occurs in coarser grained sediments, but there are few comprehensive studies of diagenesis in shales that rigorously attempt to determine if they are sources for potentially mobile constituents or if they retain those constituents within the shale body. The silicate diagenesis of a Lower Cretaceous marine mudstone, the Harmon Member, was investigated by determining the bulk chemistry, clay mineral compositions and mineral modes using standard analytical techniques and linear programming. Changes in mineralogy are observed in hemipelagic laminated mudstones (LM) that are attributable to diagenesis despite relatively constant bulk compositions. These include authigenic kaolinite formation and illitization of detrital muscovite, K-feld-spar and authigenic kaolinite. No diagenetic trends in mineralogy are observed in rapid and episodically deposited transition zone (TZ) sediments because of primary (depositional) mineralogical variability. Diagenetic changes in mineral modes for shales of the Harmon Member are small, suggesting that silicate diagenesis proceeds under relatively “closed system” conditions. The occurrence of authigenic quartz suggests that much of the Si released from the dissolution of quartz and chert is precipitated within the Harmon Member. Al, Ti, and K apparently are conserved. Burial induced increase in temperature is inferred to be the primary control on silicate diagenesis within the Harmon Member.

Scanning electron microscopy has revealed the presence of spherical, lath and platy kaolinite in gels with Si/Al atomic ratio ranging from 1.84 to 0.76 that are hydrothermally treated under different temperature and time conditions. Hemispherical structures and excavated zones, at different stages of evolution, have been observed on the surface of the gel grains, indicating that spherical particles do not precipitate from the solution but are generated from the gels. The quantity of spherical particles depends on temperature, time and the chemical composition of the starting gel. Products from starting material with Si/Al ≈ 1 yield the highest quantity of these particles. Being metastable, sphere dissolution controls the chemistry of the solution and consequently the morphology of the precipitating crystals thus producing more elongated, curved and irregular outlines when gels with Si/Al ≈ 1 are hydrothermally treated.

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.

Hydraulic conductivity tests were conducted on thirteen compacted clayey soils being used for compacted clay liners at landfills throughout the United States. The soils were prepared to various molding water contents and then compacted and permeated in the laboratory. Results of the tests show that for all of the soils, zones exist in the compaction plane (i.e., dry unit weight vs. water content) where the hydraulic conductivity is similar. These zones fall roughly parallel to contours of constant initial saturation (degree of saturation at compaction), with lower hydraulic conductivities generally occurring for conditions corresponding to higher initial saturation. Wet of the line of optimums, lower hydraulic conductivity is also attained for soils that are more plastic and have a greater quantity of fines. A regression equation was developed from the data to estimate hydraulic conductivity given the initial saturation, compactive effort, plasticity index, and clay content.

The distribution and chemical state of Si in a synthetic 2-line ferrihydrite with a Si/(Si + Fe) molar ratio of 0.11 was studied. Heat treatment under oxidizing conditions shows that Si-rich ferrihydrite is stable to 400°C. The transformation to hematite and the formation of a polymerized amorphous-silica phase occur at 850°C. At this temperature, the specific surface area decreases greatly and the average pore diameter increases, which is indicative of sintering. Heating under severe reducing conditions causes a segregation of Si from Fe and results in a mixture of elemental Fe and SiO2. Surface and structural data suggest that Si is located near the particle surface where it limits the rearrangement of Fe octahedra to form hematite.

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 adsorption of the monovalent organic cations benzyltrimethylammonium (BTMA) and benzyltriethylammonium (BTEA) to montmorillonite was studied as a function of their concentrations and ionic strength. At low ionic strength the adsorbed amounts of BTMA and BTEA reached values of the cation exchange capacity (CEC) of the clay. An increase in the ionic strength resulted in reduction in the adsorbed amounts of the organic cations, unlike the pattern observed previously with organic monovalent cationic dyes. The reduction in adsorbed amounts of BTMA and BTEA depended on the inorganic cations according to the sequence Cs+ > Na+ > Li+, which follows the sequence of binding coefficients of these inorganic cations added. The type of the anion (that is, Cl−, ClO4−, SO42-) had no effect on the adsorbed amounts. An adsorption model which considers the electrostatic Gouy-Chapman equations, specific binding and closeness of the system could adequately simulate the adsorbed amounts of BTMA and BTEA and yield predictions for the effect of the ionic strength and concentration of electrolytes. The binding coefficient employed was K = 5000 M−1 for the formation of neutral complexes of BTMA and BTEA. This value is larger than those found for the inorganic cations but is several orders of magnitude below those found for the monovalent dyes. The binding coefficients for the formation of charged complexes of BTMA and BTEA were 20 and 5 M−1, respectively. The basal spacing of the clay did not change significantly with the adsorbed amounts of both BTMA and BTEA up to the CEC.

Smectites are one of the most important groups of phyllosilicates found in soils and sediments, and certainly one of the most difficult to study. New information about the formation mechanisms, impact of structural features on surface properties, and long-term stability of smectites can best be gained from the systematic study of single-phase specimens. In most instances, these specimens can only be obtained through synthesis under controlled conditions. Syntheses of smectites have been attempted (1) at ambient pressure and low-temperature (<100°C), (2) under moderate hydrothermal conditions (100–1000°C, pressures to several kbars), (3) under extreme hydrothermal conditions (>1000°C or pressures >10 kbars), and (4) in the presence of fluoride. Of these approaches, syntheses performed under moderate hydrothermal conditions are the most numerous and the most successful in terms of smectite yield and phase-purity. Using hydrothermal techniques, high phase-purity can be obtained for beidellites and several transition-metal smectites. However, synthesis of montmorillonite in high purity remains difficult. Starting materials for hydrothermal syntheses include gels, glasses, and other aluminosilicate minerals. The presence of Mg2+ seems to be essential for the formation of smectites, even for phases such as montmorillonite which contain low amounts of Mg. Highly crystalline smectites can be obtained when extreme temperatures or pressures are used, but other crystalline impurities are always present. Although the correlation between synthesis stability fields and thermodynamic stability fields is good in many instances, metastable phases are often formed. Few studies, however, include the additional experiments (approach from under-and over-saturation, reversal experiments) needed to ascertain the conditions for formation of thermody-namically stable phases. Thorough characterization of synthetic products by modern instrumental and molecular-scale techniques is also needed to better understand the processes leading to smectite formation.

Organoclays were prepared by exchanging Ca2+ in a Ca2+-saturated smectite partially or fully with trimethylphenylammonium (TMPA) cations. The mechanistic function of these organoclays as adsorbents for neutral organic compounds in aqueous solution was examined. TMPA cations were found to take a random distribution on the surfaces of mixed Ca/TMPA-smectites. The presence of TMPA, and its random distribution, resulted in water associated with the clay surfaces being held more weakly. Apparently, the interspersing of TMPA and Ca2+ ions prohibits the formation of a stable network of water molecules around Ca2+. Water molecules associated with the siloxane surface in mixed Ca/TMPA-clays are removed during the adsorption of neutral organic compounds from bulk water, leaving only ∼11 strongly held water molecules around each Ca2+, as opposed to ∼58 water molecules in homoionic Ca2+-smectite. These results demonstrate that the amount of water associated with the clay surfaces and interlayers depends on the nature of the exchange cation(s), and not on the amount of available siloxane surface area by itself. We conclude that in TMPA-smectites the TMPA cations function as nonhydrated pillars, and sorption of organic solutes occurs predominantly on the adjacent siloxane surfaces, which are hydrophobic in nature. The water molecules around Ca2+ in mixed Ca/TMPA-smectites obscures some of the siloxane surfaces. This diminishes sorption capacity, in an amount roughly equivalent to the fraction of the CEC occupied by Ca2+, because organic solutes cannot displace the waters of hydration of Ca2+.