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.

In general, the N2-BET surface areas of sepiolite samples range from 95 to 400 m2/g depending on deposits.

The surface areas of five sepiolites, all varying in crystallite size, were measured on heating, and were compared with a model calculation. A sharp decrease in the surface area, due to crystal folding, was observed between 200° and 400°C. Both before and after the folding, each sepiolite sample had peculiar values. Our model sufficiently explains this difference in surface areas among the samples. In the model, which is based on the Brauner-Preisinger structural model, surface area is a function of the crystallite size and the ratios of the coverage for nitrogen adsorption on both the internal and external surfaces. These ratios of the coverage can be inversely estimated from the model. The ratios of the coverage on the internal surface are less than 0.19, and that on the external surface between 0.7 and 1.0.

In a previous paper, we used powder X-ray diffraction and changes in magnetic susceptibility to argue the importance of pedogenic maghemite to soils and the efficacy of the chemical extractant citrate-bicarbonate-dithionite (CBD) to preferentially remove pedogenic maghemite from soil samples while not removing coarse-grained magnetite. Although X-ray diffraction provides strong support for this contention, Mössbauer spectroscopy is the method of choice for determining the oxidation state of iron in minerals and for inferring mineralogy of the iron oxide phases. Our objective in this work was to seek confirming evidence of the importance of maghemite as a pedogenic mineral and the usefulness of the CBD procedure in separating pedogenic maghemite from lithogenic magnetite. We present Mössbauer data on magnetic fractions from pre- and post-CBD treated soil samples. Six of the 10 samples had only maghemite as the sextet component and after CBD treatment, four lost between 96 and 100% of the magnetic susceptibility. Two samples were interpreted as highly oxidized magnetite or a mixture of magnetite and maghemite. We cannot distinguish between these with Mössbauer spectroscopy. In the remaining two samples, iron existed as hematite, ilmenite, magnetite and minor (<10%) amounts of maghemite. Our results provide additional support for pedogenic maghemite in soils and for the preferential removal of maghemite by the CBD procedure.

Lower Wham Brake is a cypress, rim-swamp artificially enclosed in 1950 as a 22 km2 industrial reservoir by the International Paper Company (IPC)-Bastrop Mill, for regulating downstream water quality. Sediment cores were examined by XRD to differentiate paper-mill effluent deposition from the underlying detrital sediments and by 210Pb decay spectroscopy to determine sediment accretion rates.

Anatase and kaolin from the IPC paper-mill effluent delineated a well-defined, anthropic, silty-clay, A horizon above a clay, 2Ag horizon. Anatase concentrations were no greater than 1.7% in the A horizon and was absent in the underlying 2Agl horizon. Kaolin deposition was significantly correlated to the A horizon by an average increase of 84% above the kaolinite detrital background. Pyrite was detected in the A horizon as a transformation mineral following sulfur reduction of the paper-mill effluent.

Five of the six sediment cores showed an inflection in the excess 210Pb activity profile consistent with a present-day reduction in sediment supply. The average modern sedimentation rate was 0.05 cm yr−1. Average sedimentation observed during historic accretion was 0.22 cm yr−1, about 4.4 times greater than the modern rate of accretion. Reduction in sediment accretion can be attributed to upstream levees completed in 1934 and loss of organic accumulation following the 1950 reservoir impoundment. However, radiometric dating could not precisely correlate the geochronology of kaolin/anatase introduction due to complex oxidation/reduction cycles concurrent with the modern accretion regime.

In soil environments, the surfaces of clay minerals are often coated with hydrolytic products of Al. However, limited information is available on the effect of hydroxyaluminum coatings on the interlayering of enzymes for montmorillonite. The objective of this study was to compare the adsorption of tyrosinase onto montmorillonite as influenced by levels of hydroxyaluminum coatings. Tyrosinase is one of the strongest catalysts in the transformation of phenolic compounds. Adsorption of tyrosinase onto Ca-montmorillonite (Ca-Mte) and different hydroxyaluminum-montmorillomte complexes (Al(OH)x-Mte), containing 1.0, 2.5 and 5.0 mmol coated Al/g clay, was studied both in the absence and in the presence of a phosphate buffer at pH 6.5 and 25°C. Except for Ca-Mte in the absence of phosphate where the adsorption isotherm was of C type (linear), the adsorption isotherms were of L type (Langmuir). More tyrosinase molecules were adsorbed onto Ca-Mte than onto the Al(OH)x-Mte complexes, both in the absence and in the presence of phosphate. This indicated the easy accessibility of the enzyme to the uncoated Ca-Mte surfaces. The presence of phosphate did not significantly affect the amount of tyrosinase adsorbed onto Ca-Mte, but substantially reduced the adsorption of tyrosinase onto Al(OH)x-Mte complexes. The higher the level of hydroxyaluminum coatings, the lower the amount of tyrosinase was adsorbed. Because of their affinity to the aluminous surfaces, phosphate ions evidently competed strongly with tyrosinase for Al(OH)x-Mte complexes adsorption sites. The intercalation of tyrosinase by Ca-Mte was indicated by the increased d-spacing of the complex as the amount of the enzyme adsorbed increased. The infrared spectra of tyrosinase-Ca-Mte complex showed that the amide II band of tyrosinase at 1540 cm-1 was practically unaffected by adsorption. The amide I band at 1654 cm-1 was shifted toward a higher frequency, indicating a slight perturbation in the protein conformation. This perturbation became more noticeable in the presence of Al(OH)x-Mte complexes. The data indicated that hydroxyaluminum coatings play an important role in retarding the adsorption of tyrosinase by montmorillonite, and phosphate effectively competes with tyrosinase for the adsorption sites on Al(OH)x-Mte complexes.

Earlier interpretations of the conversion of the virgin smectite of the Ordovician Kinnekulle K-bentonites into the present mixed-layer illite/smectite imply that it took place through charge increase of the smectite with subsequent uptake and fixation of potassium. Recent analyses show that the layer charge of the smectite component of the I/S is in fact low and they suggest that neoformation of a separate illite phase took place. Pytte's kinetic model gives good agreement with the actual conversion rate for an activation energy of about 25–27 kcal/mole, depending on the adopted rate parameters, temperature history and assumed potassium source. In the Kinnekulle case the rate-controlling factor appears to have been the supply of potassium, which is concluded to have required large-scale, heat-induced groundwater convection.

Experimental alterations of K-feldspar in distilled-deionized water at 150°, 175°, 200°, and 225°C were performed. The alteration products and dissolution mechanism of K-feldspar were examined by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX), and X-ray photoelectron spectroscopy (XPS). SEM, TEM, and EDX clearly showed formation of fibrous boehmite less than 1.0 μm in length at the early alteration stages. The boehmite fibers decreased in abundance and rounded platy 1 M mica was produced as alteration proceeded. The mica exhibited initially angular shaped small flakes of 0.69 μm in average size, which developed to rounded platy particles of 1.97 μm. The main chemical reactions occurring in this experimental system can be expressed by: $$\begin{array}{l} \mathop {KAlS{i_3}{O_3}}\limits_{\left[ {K - feldspar} \right]} + 6{H_2}O + {H^ + } \to \mathop {AlO\left( {OH} \right)}\limits_{\left[ {boehmite} \right]} + 3{H_4}Si{O_4} + {K^ + }, \\ \mathop {3KAlS{i_3}{O_8}}\limits_{\left[ {K - feldspar} \right]} + 12{H_2}O \to \mathop {KA{l_3}S{i_3}{O_{10}}{{\left( {OH} \right)}_2}}\limits_{\left[ {mica} \right]} + 2{K^ + } + 6{H_4}Si{O_4} + 22{H^ + }. \\ \end{array}$$ XPS showed no significant changes in intensities of photoelectron lines excited from K, Si, and Al in the K-feldspar surface before and after alteration, however the K/Si molar ratios in the solutions were considerably smaller than that of the original K-feldspar. The results of XPS strongly indicate that no dealkalized layer was produced on the surface, and that dissolution of K-feldspar in aqueous solution proceeded congruently by a surface-reaction mechanism. The discrepancy of mass balance in the solutions may be mainly caused by adsorption of K on the surface of boehmite.

The bonding in a cronstedtite layer was studied using a ninefold ordered supercell band structure calculation. The tight-binding scheme based upon the extended Hückel method was used to predict the electronic structure. The size of the problem was 162 atoms with 798 valence orbitals. The calculation showed different orbital interactions of oxygen p-orbitals with neighboring atoms with respect to the position in the layer. Substitution of Fe for Si in the terahedra reduced the role of the valence p-orbitals of the central Fe atoms. The d-orbitals of Fe were split in accordance with the rule of t2g-eg splitting. Although the density of states at the Fermi level was high, the partially filled 3d-bands were too narrow to permit normal metallic conduction.

The three-dimensional crystal structure of rotationally disordered illite/smectite (I/S) in K-bentonite samples from the Appalachian basin and neighboring areas is described using the parameters of 1) P0, the proportion of zero-degree layer stacking rotations, such as in the polytype series 1Md-1M; 2) Pcv, the proportion of 2:1 layers with cis-vacant (cv) octahedral sites that are randomly interstratified with trans-vacant (tv) layers; and 3) P60 the proportion of layers with n·60° rotations (as opposed to n·120°) in the rotated layers. These parameters were determined by computer modeling of experimental randomly oriented powder X-ray diffraction patterns.

The proportion of cv interstratification in the I/S increases with A1 and decreases with Mg and Fe content. The proportion of n·60° rotations in the rotated layers increases with Mg and Fe content. The cv 120° disordered structure correlates with tetrahedral A1 for Si substitution and increasing tetrahedral charge. The tv n·60° disordered structures correlate with octahedral Mg for A1 substitution. The data indicate that the type of unit cell and nature of rotational disorder in I/S is controlled by the octahedral Mg content. The three-dimensional structures do not show any systematic correlation with Reichweite and percent expandability as determined from diffraction patterns of oriented sample preparations.

While soils formed in tephra are typically dominated by poorly crystalline clay minerals, the occurrence of smectite in E horizons of podzolized soils (Spodosols) has been well-documented. We have observed a well-crystallized smectite mineral dominating the clay fraction of E horizons in tephra-derived soils of northern Idaho. This study was initiated to examine properties and distribution of this mineral along a developmental sequence of high-elevation, forested Spodosols formed in 6800-yr-old Mazama tephra. Three soils exhibiting strong, moderate, and weak E horizon development were sampled along an elevational and climatic gradient. The smectite mineral was identified as beidellite based on expansion and layer charge characteristics. Heated, Li-saturated samples from the most strongly developed E horizon exhibited relatively complete expansion to 1.8 nm with glycerol solvation and mean layer charge was calculated to be 0.44 molc/formula unit using sorption characteristics of alkylammonium ions. Apparent crystallinity and relative abundance of the beidellite in clay fractions decrease with decreasing E horizon development. The more poorly crystalline beidellite is associated with a non-expansive 1.4-nm mineral with considerable Al-hydroxy interlayering. Beidellite was not detected in underlying glacial drift or in a thin layer of 200-yr-old ash that mantles these soils, suggesting it is not inherited from these materials. Rather, our results indicate that beidellite forms in these soils in an environment characterized by low pH and a large flux of organic metal-complexing agents.

Several samples of large- and small-particle magnetite (Fe3O4), as well as its thermal decomposition products formed at different temperatures and atmospheres, have been studied extensively by Mössbauer spectroscopy (MS), both with and without an applied field of 6T. Synthetic mixtures of magnetite and poorly- or well-crystallized maghemite have also been studied. Large-particle magnetite (MCD > 200 nm), when heated in air for 12 hours at T < 400°C, transforms to a mixture of well-crystallized hematite and magnetite, the latter one remaining stoichiometric, according to the relative area-ratios obtained from MS. Thermal treatment at 1300°C in a controlled O2 partial pressure, produced a mixture of stoichiometric and nonstoichiometric magnetite, but the latter component seems to be composed of particles with different degrees of nonstoichiometry. The Mössbauer spectra of the decomposition products at T < 200°C in air of small-particle magnetite (MCD ~ 80 nm) could be successfully interpreted as a mixture of magnetite and maghemite, rather than nonstoichiometric magnetite. This suggestion is further supported by the experiments with the synthetic mixtures. It is clearly demonstrated that is not possible, even by applying a strong external field, to separate the contribution of the A-site of magnetite from that of maghemite.

—The charge of the expandable interlayers in a series of fourteen diagenetic illite/smectites (I/S) from lower Paleozoic K-bentonites was determined by the alkylammonium ion exchange method. The magnitude (<0.50 equivalents per half formula unit) and characteristic heterogeneous distribution of interlayer charges in eight samples with expandabilities from 70% to about 15% confirm the smectitic character of the expandable interlayers in this range. This result coupled with the lack of a correlation between expandability and interlayer charge is consistent with the hypothesis of a layer-by-layer transformation from a precursor smectite to highly illitic I/S clays during K-bentonite diagenesis. The charge of the expandable interlayers in I/S samples with about 10% or less expandabilities have been inferred to be vermiculitic rather than smectitic. The K-fixed interlayers and expandable interlayers in these samples appear to be similar in charge. The significantly higher charges inferred for the highly illitic samples can be consistent both with a layer-by-layer transformation and the neoformation mechanisms proposed in the literature for the formation of illite.

The association between clay silicates, and iron and aluminium oxides has a major influence on the chemical and physical properties of soils. In this work the interaction of a kaolin substrate with iron and aluminium oxides and/or hydroxides obtained by basification of solutions of the metal ions was compared to that of quartz. Both precipitates were obtained in the presence of the substrates.

The aluminium precipitates had higher crystallinity, and thus led to smaller increases in specific surface area than those of iron, and were more effective modifiers of the surface electrical properties of the kaolin-oxide mixtures. At concentrations as low as 0.43% Al (g/100 g of substrate) the point of zero charge (PZC) of the components with variable charge was measurable, while Fe required 2.23% and gave lower PZCs than those of corresponding concentrations of Al. In both cases the PZCs shifted to higher pH as metal concentration was increased, as did the flocculation interval of colloidal suspensions of kaolin, which were close to the PZCs (where these were evaluated).

The Al and Fe oxides precipitated on quartz had higher crystallinities. Both metals increased the specific surface area to a similar extent, with an almost linear relationship to metal concentration. Samples containing ca. 6.5% Fe or Al had similar or slightly higher PZCs than corresponding kaolin samples.

The results were interpreted by assuming, in the case of kaolin, the union of the metal precipitate with the basal faces of the substrate, so decreasing the negative charge at this surface; and in the case of quartz, the formation of a hydroxide coating that neutralizes the negative charge on the silica surface. The difference between the results obtained for each metal was attributed to the different morphologies of their oxide precipitates.

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 objective of this study was to observe flocculation of montmorillonite in the presence of a glucose polymer (dextran) and to observe the effect of saturating cation and coagulant addition on the flocculation process. Flocculation of montmorillonite was dependent on polymer molecular weight, polymer/clay ratio (w/w), nature of exchangeable cation, and ionic strength of the suspension to which the polymer was added. The T500 dextran (molecular weight = 5 × 105) caused enhanced sedimentation of Ca-montmorillonite suspension at a polymer/clay ratio of ≤0.01. Increasing the polymer concentration above this level stabilized the suspension such that sedimentation was less than or equal to that of the control. The T2000 dextran (molecular weight = 2 × 106) caused a similar increase in the sedimentation of Ca-montmorillonite at polymer/clay ratios of <0.1. The ability of the T2000 polymer to cause flocculation at greater polymer/clay ratios as compared to the T500 polymer was attributed to the lower osmotic pressure between clay particles for equal concentrations of the two polymers. Flocculation of Ca-montmorillonite by dextran was enhanced when the clay had initially been coagulated by the addition of salt. Reduction of the diffuse double layer upon addition of salt permitted the polymer to extend beyond the electrostatic barrier of the clays. Dextran was not able to flocculate Mg-montmorillonite suspensions with or without the presence of coagulant. The displacement of water molecules at the clay surface rather than within the hydration shell of the more highly polarizing Mg cations by polymer segments resulted in a greater polymer collapse on the clay surface leaving fewer and shorter polymer loops and tails available for contacting adjacent clay particles.

Monte Carlo (MC) simulations of molecular structure in the interlayers of 2:1 Na-saturated clay minerals were performed to address several important simulation methodological issues. Investigation was focused on monolayer hydrates of the clay minerals because these systems provide a severe test of the quality and sensitivity of MC interlayer simulations. Comparisons were made between two leading models of the water-water interaction in condensed phases, and the sensitivity of the simulations to the size or shape of the periodically-repeated simulation cell was determined. The results indicated that model potential functions permitting significant deviations from the molecular environment in bulk liquid water are superior to those calibrated to mimic the bulk water structure closely. Increasing the simulation cell size or altering its shape from a rectangular 21.12 Å × 18.28 Å × 6.54 Å cell (about eight clay mineral unit cells) had no significant effect on the calculated interlayer properties.

The illitic end of mixed-layer illite-smectite series (I/S) in shales from Lower Cretaceous Barra de Itiúba Formation, Sergipe-Alagoas basin, was examined with X-ray powder diffraction (XRD) and transmission electron microscopy (TEM). A mathematical decomposition of XRD patterns shows different I/S and illite populations. All the samples contain ordered (R = 1) I/S, poorly crystallized illite (PCI) and well crystallized illite (WCI). A randomly interstratified (R = 0) I/S was also identified in a fractured zone at 1020 m. The percentage of expandable layers in ordered I/S decrease progressively from 20% to 10%. TEM observations show a continuous change in morphology between two basic particle shapes: elongated (lath) and isometric. The size and morphology of particles change with increasing depth. The proportion of laths decreases while isometric particles become predominant. However, both particle types continuously grow and enrich the larger size fraction. The growth process is driven by a mass transfer from the dissolving small particles of predominantly I/S (R = 1) composition to the larger (more illitic) lath and isometric ones. The proportion of lath-shaped particles decreases with depth indicating that the more stable population upon increased burial is the isometric well crystallized illite (WCI) particles. Very large laths are observed in the fault zone where conditions may favor faster growth processes.

Fine-grained biotite crystals within primary actinolite from a quartz monzonite body of the Bingham Canyon porphyry copper deposit, Utah, consist of 1M, 5M1, and 1Md polytype structures. HRTEM images directly show the stacking sequences of ordered biotite polytypes, stacking faults in ordered polytypes, and stacking sequences in disordered polytypes, if the stacking vectors for the 2:1 layers involve only 0° and ± 120° rotations. The most common type of stacking fault in the 1M biotite is a layer with −120° rotation, followed by a layer with +120° rotation, which corresponds to one unit cell of the 2M1 polytype inserted in the 1M structure. Disordered (or semi-random) biotite is composed primarily of thin domains of the 1M and 2M1 polytypes, with stacking faults. The structure of a new 5-layer (5M1) polytype has been determined from SAED and HRTEM results. The stacking sequence of the polytype is [02022].

A model of structural oscillation among 1M, 2M1, and 3T structural states is proposed to interpret nonperiodic stacking sequences in biotite crystals formed during non-equilibrium crystallization. The model also provides qualitative insights into the structure of complex long-period polytypes and may help to explain intergrowths of ordered and disordered polytypes that form during crystallization far from the equilibrium state.

The mode of growth of authigenic, lath-shaped illitic particles has been investigated using field emission scanning electron microscopy (FESEM) and high resolution transmission electron microscopy (HRTEM). Two types of clay lath have been identified: overgrowths on platelets of illite or illite-smectite and discrete particles. Both are neoformed and show a slight increase in abundance with depth over the 70 m depth interval sampled. Interpretation of lattice fringe data is not unambiguous but indicates that the clay is either illite or illite-smectite with R1 structure. The formation of discrete particles of authigenic illite, or even R1 illite-smectite, is compatible with present burial depths and a regional geothermal gradient of approximately 40°C/km. This illite also differs from many previous reported occurrences of authigenic illite in mudrocks in that it appears to have formed, without being preceded by progressive illitization of illite-smectite.

The surface microtopography of hematite over the course of dissolution in oxalic and citric acids was examined by in-situ and ex-situ atomic-force microscopy. In-situ imaging of the basal-plane surface of a centimeter-scale natural hematite sample immersed in 2 mM citric acid demonstrated that the basal-plane surface was relatively unreactive; rather, dissolution occurred along step edges and via etch-pit formation. Ex-situ imaging of synthetic hematite particles following batch dissolution in 1 mM oxalic acid showed similar dissolution features on basal-plane surfaces; in addition, etching along particle edges was apparent. The presence of etch features is consistent with a surface-controlled dissolution reaction. The results are in agreement with previous investigations suggesting that the basal-plane surface is relatively unreactive with respect to ligand exchange. Both in-situ and ex-situ imaging of particle surfaces can provide valuable information on the roles of surface structures and microtopographic features in mineral dissolution.