bluuebunny/crossref_metadata_2025 huggingface dataset:
The Release of Aluminum from Aluminosilicate Minerals. II. Acid-Base Potentiometric Titrations
Authors: Cabrera F. , Talibudeen O.
Published: August 2006

Acidified suspensions of Al-saturated kaolinite, montmorillonite, mica, illite, and biotite in 10−3 M NaNO3 were potentiometrically titrated with 0.1 N NaOH and 0.1 N HNO3 in succession in a CO2-free nitrogen atmosphere. The resulting curves were compared with those for Al(NO3)3 solutions of similar Al concentration in the supernatant solution and corrected for Al in the entrained solution in the clay.

Base titrations of Al ions adsorbed on all the minerals, except montmorillonite, showed two pH inflections separated by a buffering range. With montmorillonite, there were three pH inflections similar to those for Al in solution. The first inflections in the titration of suspensions occurred at lower pHs and were less pronounced than for Al in solution. These represent the titration of H3O+ sorbed during the pretreatment. The buffering by adsorbed Al ions is also less than that by Al in solution.

The OH− used up by adsorbed Al ions between the first and last inflections was equal to, or slightly greater than, the CEC of the minerals, except for mica where it was more than twice the CEC, because new interlayer surfaces were formed during the acid pretreatment. Acid titration curves of Al ions in the adsorbed and solution states showed hysteresis when related to the base titration curves. The use of two titration speeds (3 and 0.3 pH units/hr) only slightly affected the titration curves of the minerals suggesting that the observed effects were not caused by lack of equilibrium with added base or acid.
High Surface Area Solids Obtained by Reaction of Montmorillonite with Zirconyl Chloride
Authors: Yamanaka S. , Brindley G. W.
Published: August 2006

Exchange reactions of Na-montmorillonite with zirconyl chloride solutions give products with basal spacings near 18 Å which are stable to 500°C and have surface areas of the order of 300–400 m2/g. The Na ions are exchanged with tetrameric hydroxy cations [Zr4(OH)14•nH2O]2+. The high surface area is attributed to the porosity formed by stable zirconium oxide “pillars” formed by dehydroxylation of the complex cation. The nitrogen adsorption isotherms are of Langmuir type and are consistent with adsorption in interlayer micropores. Reduced-charge montmorillonites, formed by application of the Hofmann-Klemen procedure, give either similar or slightly smaller surface areas.
Ideal Behavior in Na+-Trace Metal Cation Exchange on Camp Berteau Montmorillonite
Authors: Sposito Garrison , Mattigod Shas V.
Published: August 2006

The conditions under which an exchanger phase will behave as an ideal mixture are established from thermodynamic principles. It is shown that, if a stoichiometric cation-exchange reaction is reversible, the exchanger phase will exhibit ideal behavior if the Vanselow selectivity coefficient is independent of the exchanger composition. This criterion is applied to some recently published data for Na+-trace metal cation exchange on Camp Berteau montmorillonite. An analysis of the data suggests that, so long as the exchange process is reversible, Na+-trace metal cation exchange produces an exchanger phase that behaves as an ideal mixture.
Reactivity of Adsorbed and Structural Iron in Hectorite as Indicated by Oxidation of Benzidine
Authors: McBride M. B.
Published: August 2006

The roles of different forms of Fe(III) impurities in a hectorite with respect to the oxidation of benzidine in aqueous suspension have been evaluated using electron spin resonance and UV-visible spectroscopy. Natural surface-adsorbed Fe(III) showed no detectable activity in the oxidation process, while very small quantities of structural octahedral Fe(III) apparently promoted a relatively rapid conversion to the radical cation. However, extremely small quantities of benzidine were oxidized in comparison to the exchange capacity of the clay. Freshly adsorbed Fe3+ cations effectively oxidized benzidine, but lost much of this ability upon aging. The Fe(III)-benzidine electron transfer could be distinguished from an O2-benzidine reaction, since the latter reaction was slow and limited by the rate of O2 diffusion into the clay-water system. The O2-benzidine reaction was also inhibited at high pH. The existence of two reaction mechanisms and the involvement of only a small fraction of the total structural iron, as shown by comparison of the hectorite and a montmorillonite, may explain the conflicting interpretations in the literature. The benzidine blue reaction not only requires an oxidizing agent to form the radical, but also a clay surface to adsorb and stabilize it against further oxidation.
Cation Ordering Pattern in Amesite
Authors: Hall Stephen H. , Bailey Sturges W.
Published: August 2006

Cation ordering in amesite-2H2 from Antarctica has reduced the true symmetry from the ideal hexagonal space group P63 to triclinic P1. All crystals show 6-fold biaxial twin sectors on (001), and the twinned crystals produce an average diffraction symmetry that is hexagonal. Individual twin sectors cut from the larger aggregate have 2 V optic angles near 18°, slightly monoclinic unit-cell geometry, and triclinic diffraction symmetry. Structural refinement of an untwinned sector in subgroup symmetry shows nearly complete ordering of Si,Al in tetrahedral sites and of Mg, Al in octahedral sites.

In triclinic symmetry the two layers in the unit cell are no longer equivalent. Tetrahedra lying on the pseudo-63 screw axis are alternately Si-rich and Al-rich in adjacent layers. Of the three octahedral sites in each layer, one is smaller than the other two and is interpreted as Al-rich. The distribution of Al-rich and Mg-rich octahedra violates both the pseudo-3-fold rotation axis within each layer and the pseudo-63 screw axis that relates one layer to the next in the ideal space group. Local charge balance is achieved in adjacent layers by location of all tetrahedral and octahedral Al in lines parallel to X1 and spaced at intervals of b1/2. Similar charge balance patterns parallel to X2 and X3 are postulated to account for the sector twinning, which has been observed also in amesites from Chester, Massachusetts, USA, Saranovskoye, USSR, and Postmasburg, South Africa.
The Hydrothermal Transformation of Sepiolite to Stevensite and the Effect of Added Chlorides and Hydroxides
Authors: Güven Necip , Carney Leroy L.
Published: August 2006

Hydrothermal reactions in the system sepiolite/H2O have been examined between 149° and 316°C. Approximately 10–20% of the starting sepiolite was converted to a smectite (stevensite) at 204°C within 24 hr. Similar results were obtained when CaCl2, NaOH, Ca(OH)2, or Mg(OH)2 was added to the system. In the presence of NaCl, about 60% of the sepiolite was converted to stevensite, whereas, only 5% stevensite formed in the presence of MgCl2. Greater amounts of stevensite formed at 260°C in these systems. Above 316°C, 60–80% of the sepiolite was converted to stevensite in 24 hr, regardless of the presence or absence of salts. Within the experimental conditions used, temperature is the most important factor in the sepiolite-to-stevensite conversion.

At or below 216°C, sepiolite appears to transform into stevensite by dislocations involving c12 glides that are triggered by the stresses of the hydrothermal conditions. Above this temperature, stevensite seems to form by direct precipitation after dissolution of sepiolite.
Estimate of Clay-Mineral Content: Additions of Proportions of Soil Clay to Constant Standard
Authors: Ruhe Robert V. , Olson Carolyn G.
Published: August 2006

The method of known additions for estimating clay-mineral content was reversed in that increasing proportions of soil clay were added to a standard composed of equal weights of kaolinite, illite, and montmorillonite. After glycolation, peak-area ratios were calculated from 7.2 (kaolinite), 10 (illite), 14 and 17 Å (vermiculite and montmorillonite) diffraction peaks of standard, mixes, and soil clay. Ratios were plotted against % soil clay from the standard (0%) through the mixes (14 to 77%). Curves of fit were calculated and projected to 100% soil clay giving theoretical values which agree with measured values. As weight proportions are known in the standard, the projections permit estimates of clay-mineral weight proportions in the soil clay.
Thermodynamic and Structural Features of Water Sorption in Zeolites
Authors: Simonot-Grange Marie Hélène
Published: August 2006

The water adsorption capacity of zeolites is a function of pressure and temperature. Desorption of zeolites may be of three types, wherein the crystal lattice undergoes (1) no or little change, (2) a reversible change, or (3) an irreversible change. In the first two cases, the divariance of the zeolite-water vapor equilibrium results in networks of isobars, isotherms, and isosteres which can be transformed into a “characteristic” curve following the Polanyi-Dubinin theory. Because the volume of the micropores of a zeolite structure is constant, the isotherms and “characteristic” curve can be transformed linearly. During desorption, if the volume of the micropores varies due to a change of structure, the curves show linearity breaks.

On the basis of X-ray diffraction, differential thermal, and thermal gravimetric analyses, the equilibrium curves and structural changes of heulandite and stilbite were determined, using specially designed equipment. In the reversible adsorption range, heulandite shows no linearity breaks in the transforms and no structural variation. Stilbite, however, shows a linearity break in the transforms corresponding to a structural change.
Clay-Polymer Interactions: Summary and Perspectives
Authors: Theng B. K. G.
Published: August 2006

The adsorption of uncharged polymers by clays is largely “entropy-driven.” Polymer conformation changes from a random coil in solution to an extended form at the surface in which adsorbed polymer segments or trains alternate with loops and tails extending away from the surface. Although the net interaction energy, ε, per segment-surface contact is small (~1 kT unit), the total energy of adsorption is large because the fraction of train segments, p, is commonly between 0.3 and 0.5. The adsorption isotherms are typically of the high-affinity type, and there is an apparent lack of desorption on dilution. Positively charged polymers (polycations) are adsorbed largely through electrostatic interactions between the cationic groups of the polymer and the negatively charged sites at the clay surface. Here ε ≫ 1 kT unit and p > 0.7, leading to an almost complete collapse of the polymer chain onto the surface. Indeed, beyond a given level of adsorption charge reversal can occur in that the clay-polycation system effectively behaves as an anion exchanger. Little adsorption occurs with negatively charged polymers (polyanions) due to initial charge repulsion between the polymer and the clay surface. Acid pH, a high ionic strength, and the presence of polyvalent cations in the system enhance and promote polyanion adsorption. Uncharged polymers and polycations can enter the interlayer space of expanding 2:1 type layer silicates but polyanions generally fail to intercalate.

The interactions of clays with biopolymers, such as proteins, nucleic acids, and polysaccharides, can be rationalized in similar terms. When intercalation occurs, the interlayer biopolymer is further stabilized against microbial (enzymatic) degradation giving rise to practical applications of clay-polymer complexes as flocculants and soil conditioners. Polyanions are effective as flocculants because of their large “grappling distance,” whereas uncharged polymers are better suited as soil conditioners because they can spread over adjacent clay/soil particle surfaces like a coat of paint.
Anion Interactions with Freshly Prepared Hydrous Iron Oxides
Authors: Harrison Jeffrey B. , Berkheiser Vaughn E.
Published: August 2006

Infrared analysis showed that the bonding habit of oxyanions with freshly precipitated hydrous ferric oxides depends upon the nature of the anion and its hydration level. Monovalent oxyanions adsorb through an electrostatic interaction with the hydrated hydrous oxide surface. All divalent oxyanions, with the exception of tellurate, coordinate directly with surface iron cations. Tellurate, an octahedral anion, apparently penetrates and incorporates in the hydrous oxide structure. The symmetry of the free anion has a significant role in determining the configuration of the resultant complex. For anions of the same charge, those with tetrahedral geometry (in uncoordinated states) show a higher degree of specificity for the surface than the trigonal planer anions. Without exception, each bidentate bridging complex forms by replacement of protonated and unprotonated hydroxyls. With the anion geometry and the charge being equal, the suspension pH determines the adsorption capacity of the hydrous oxide.
Influence of Silica Content on the Surface Charge Characteristics of Allophanic Clays
Authors: Gonzales-Batista A. , Hernandez-Moreno J. M. , Fernandez-Caldas E. , Herbillon A. J.
Published: August 2006

The surface and charge characteristics of 6 allophanic clays originating from a climatosequence of Andisols have been studied by titration, ion retention, surface area, and reactivity measurements. Several properties of these clays, such as the pH of zero charge, the magnitude of the surface area, and the reactivity of structural hydroxyl groups, appear to be governed by their chemical composition, especially by their silica content. A similar relationship between the above properties and silica content also exists for synthetic aluminosilicate gels (often quoted in the literature as possible models of allophanes), despite their different structure to the natural clays. An explanation is that as desilication proceeds, octahedral polymeric units of aluminum progressively individualize in both the synthetic and natural samples. The surface areas of the aUophanic clays, based on the slope of the titration curve at pH 7, are closely related to the amounts of structural hydroxyl that can react with fluoride at about the same pH. The permanent negative charges are always very low, even for silica-rich, allophane-bearing samples. It is therefore suggested that all of these clays should be virtually free of tetrahedral aluminum.
Synthesis of Methyl-t-Butyl Ether from Methanol and Isobutene Using a Clay Catalyst
Authors: Adams J. M. , Clement D. E. , Graham S. H.
Published: August 2006

The acid-catalyzed reaction between methanol and isobutene to give methyl-t-butyl ether may be carried out using a cation-exchanged smectite as the catalyst. In 1,4-dioxan solvent at 60°C smectites exchanged with Al3+, Fe3+, or Cr3+ give yields of ∼60% after 4 hr, whereas smectites exchanged with Cu2+, Pb2+, Ni2+, Co2+, Ca2+, and Na+ give less than ∼8% yield. The reaction is efficient only when certain solvents are used, e.g., with Al3+-smectite the yield is ∼5% when using 1,2-dimethoxyethane, diethyleneglycol diethylether, n-pentane, tetrahydropyran, N-methylmorpholine, or tetrahydrofuran solvents compared with ∼60% using 1,4-dioxan solvent (4 hr). Moreover, the effective solvents depend somewhat on the clay interlayer cation. The use of tetrahydrofuran and tetrahydropyran gives ∼35% yields at 60°C (4 hr) with Fe3+- or Cr3+-smectites but ∼4% yield with Al3+-smectite.
Natural Ammonium Illites from Black Shales Hosting a Stratiform Base Metal Deposit, Delong Mountains, Northern Alaska
Authors: Sterne Edward J. , Reynolds Robert C. , Zantop Half
Published: August 2006

Naturally occurring ammonium illites have been discovered in black shales surrounding a stratiform base metal deposit in the DeLong Mountains, northern Alaska. Infrared spectra of the samples exhibit pronounced absorption at 1430 cm−1, the resonant-banding frequency for NH4+ coordinated in the illite interlayer. X-ray powder diffraction characteristics of the ammonium illites include an expanded d(001) spacing, with values as large as 10.16 Å, and ratios for I001/I003 and I002/I005 of about 2. Infrared analyses of physical mixtures of NH4Cl with a standard illite, and comparisons with synthetic ammonium micas indicate significant substitution (>50%) of NH4+ for K+ in the illite interlayer position. Nitrogen determinations on two ammonium illites after removal of carbonaceous matter gave values of 1.48 wt. % NH4+ and 1.44 wt. % NH4+. A survey of more than 150 different shale horizons indicates that the NH4+ content of the illites increases in proximity to the stratiform base metal mineralization.
Adsorption of Alkylphosphoric Acid on Kaolinite and Smectite in Water-Decane
Authors: Siffert B. , Trescol J. J.
Published: August 2006

Bis-ethyl 2-hexylphosphoric acid (di-2 EHPA) dissolved in decane is chemisorbed on kaolinite and montmorillonite dispersed in an acidic aqueous solution. The adsorption results in the formation of complexes with the surface cations of the clays. The adsorption isotherms are of the Langmuir type and reveal a limiting value of adsorption on H+-kaolinite of 12.2 mg/g, comparable to that measured in the absence of water. For H+-montmorillonite, however, the limiting value in the presence of acid is somewhat less (20.6 mg/g vs. 23.8 mg/g). Di-2 EHPA does not react with the magnesium cations available at the surface. The isotherm is “stepped” and suggests the presence of adsorption sites with distinctly differentiated energies. The sites of di-2 EHPA adsorption can be masked by treating the two clay minerals with polyphosphate anions. Thus, with pyro- and tripolyphosphate anions, di-2 EHPA uptake in acidic medium is very low. Adsorbed di-2 EHPA can be recovered by treating the clays with fluoride, hydroxyl, and dihydrogenphosphate anions. Dihydrogenphosphate anions lead, however, to a state of equilibrium between the organic and inorganic phosphate anions adsorbed.
Palygorskite-Sepiolite Clays of Lebrija, Southern Spain
Authors: Galan E. , Ferrero A.
Published: August 2006

The Upper Pliocene sediments near Lebrija in southern Spain contain commercial deposits of palygorskite and sepiolite. These sediments of continental origin consist chiefly of carbonate, marl, and clay resting on marine Pliocene quartzose sand. The lowest unit, the “Marly-Calcareous Bed,” consists of sepiolite-rich marl associated with concretions and irregular layers of chert, <0.5 m thick, and local diatomite layers, as well as limestone, sandy limestone, marl, and clayey sandstones. This unit has a maximum thickness of 30 m and contains three clay-mineral suites as follows: (1) bottom—sepiolite ± palygorskite; (2) center—sepiolite and palygorskite ± illite; (3) top—palygorskite and illite, ± sepiolite and smectite. Sepiolite decreases and palygorskite and illite increase toward the top, reflecting the composition of detrital material supplied to the basin. Beds 0.5–1 m thick locally and containing 50 to 60% sepiolite have been called “Tierra del Vino” (wine earth) because the material formerly was used to clarify and purify wine. The sepiolite-rich beds are as much as 15 m thick in the eastern part of the area. The upper unit is called the “Palygorskite Bed” because certain layers, 0.3 to 3 m thick, contain 35 to 75% palygorskite. The palygorskite-rich layers are interbedded with limestone and marl, and the entire unit is 15 m thick. The total resource of palygorskite is estimated at about 9 million tonnes.

The sediments are believed to have been deposited in a brackish, lacustrine environment. Originally, tectonic stability and an arid climate favored the formation of sepiolite at about pH 8. Later, after significant weathering of the source rocks, detrital illite was transformed to palygorskite in the Mg- and Si-rich waters. Here, palygorskite was also precipitated directly.
Transformation of Iron-Bearing Kaolinite to Iron-Free Kaolinite, Goethite, and Hematite
Authors: Rozenson Israel , Spiro Baruch , Zak Israel
Published: August 2006

Ferruginous clay partings in limestones of the marine, largely evaporitic, Upper Triassic Mohila Formation (Makhtesh Ramon, Israel) contain hexagonal plates and cube-like bodies up to one millimeter across. Analyses by electron microscopy, infrared and Mössbauer spectroscopy, and X-ray powder diffraction indicate that the matrix contains Fe-rich anhedral kaolinite, up to 100 μm in size; the hexagonal plates are composed of euhedral, Fe-free kaolinite covered with well-developed acicular goethite and platy hematite (0.5 to 2 μm in size), and the cubes consist of fine-grained goethite with minor amounts of kaolinite. The anhedral kaolinite appears to be detrital, the hexagonal plates to be authigenic, and the cubes to be pseudomorphs after pyrite. Oxidation appears to have altered Fe-rich kaolinite and pyrite to Fe-free kaolinite, goethite, and hematite and was accompanied by recrystallization and pseudomorphic replacement. The alteration process was slow and was probably induced by a small increase in pH and in the Al/Fe ratio, resulting from oxidation of reduced components (pyrite, ferrous carbonate, organic matter) in a semiclosed, sediment-mud system. Overlying kaolinitic flint clay deposits may be the final product of a similar process.
Clay Minerals in the 1980 Deposits from Mount St. Helens
Authors: Pevear D. R. , Dethier D. P. , Frank D.
Published: August 2006

Phyllosilicates are major components of the <2-μm fraction (1–3 wt. % of most bulk specimens) in more than 50 samples of air-fall tephra from several 1980 eruptions of Mount St. Helens. In all samples, trioctahedral smectite is the major clay mineral. The integral series of 00ℓ reflections in ethylene glycol-treated samples indicates a lack of interstratification; absence of a peak near 5 Å after heat treatment, the 060 peak at 1.54 Å, and energy dispersive chemical analyses indicate that the smectite is a Mg- and Fe- rich, trioctahedral saponite. Minor mica and chlorite are present in the <2-μm fraction of most samples, and some samples show a peak near 12 Å after heating to 550°C which is probably due to the presence of an interstratifled chlorite/collapsed smectite or chlorite/collapsed vermiculite. The tephra contains glass and crystals originating from new magma and lithic fragments incorporated from the pre-existing cone. The clay minerals in the tephra are lithic components stripped from older, hydrothermally altered rocks during explosive ejection. Cleaned pumice fragments, which are new magmatic components, lack smectite, but contain rare biotite in xenoliths. Old, hydrothermally altered rocks from the volcano's summit and from the debris-avalanche (former north flank) contain saponite together with chlorite and chlorite/smectite which may have formed from it. Saponite and zeolites that precipitated from neutral to alkaline hydrothermal solutions line cavities in some of these rocks. The saponite was probably not subjected to magmatic temperatures because heating this material for 5 min at 750°C collapses it irreversibly to 10 Å. Kaolinite, alunite, and opal, indicative of acid-sulfate alteration, were found only in the pre-1980 summit crater and the southwest thermal area, but were not evident in the lithic components of the 1980 deposits.
Smectite in Marine Quick-Clays of Japan
Authors: Egashira Kazuhiko , Ohtsubo Masami
Published: August 2006

Clayey sediments of marine origin having sensitivities (ratio of undisturbed to remolded shear strength) as high as 1000 at a reduced salt concentration are found around Ariake Bay, Kyushu, Japan. The clay fraction of the sediments contains smectite as a principal mineral (33–42%) in contrast to the illitic composition of most previously described quick-clays. However, this smectite is a low-swelling type, and the Na-form expands only to about the same extent as the Ca-form and gives a sediment volume almost equal to that of the Ca-clay. This low-swelling smectite appears to consist of packets of unit layers even after saturation with Na, and thus reacts like the kaolinite or illite of conventional quick-clays.
Effect of the Removal of Reactive Surface Material on the Solubility of Synthetic Gibbsites
Authors: Bloom P. R. , Weaver R. M.
Published: August 2006

The solubility of four different gibbsite preparations was measured, including two commercial hydrated aluminas produced by Alcoa, a Fisher ACS-grade Al(OH)3, and a laboratory preparation. The Alcoa samples and the laboratory-prepared sample had been studied previously by other investigators but without using a long-term acid treatment. Scanning electron microscopy showed globular surface material that was removed by a 14-day, 0.1 M HCl treatment. Solubility was determined at pH 4 from both over-and undersaturation with continuous agitation for 228 days. The acid treatment correlated with a decrease in log*Kso[*KSO = (Al3+)/(H+)3] of about 0.5 units. The mean solubility of the three acid-treated commercial gibbsite samples was log*Kso = 7.55 ± 0.055 (*Kso = 3.5 × 107). The solubility of the acid-treated laboratory preparation was log*Kso = 7.86 (*Kso = 7.2 × 107). The greater solubility of the laboratory-prepared gibbsite is attributed to a greater concentration of structural defects in the crystals.
Structural Model for Benzidine-Vermiculite
Authors: Slade P. G. , Raupach M.
Published: August 2006

A combination of X-ray diffraction, infrared, and chemical data has established that the ion exchange of vermiculite with singly charged benzidine cations in an aqueous solution at pH 1.6 results in a black, highly ordered benzidine-vermiculite intercalate. The intercalate has a basal spacing of 19.25 Å and a primitive unit cell with “a” and “b” edges parallel and equal to those of vermiculite. The number of benzidine molecules per cell is equal to its electric charge. In this structure the benzidine molecules are steeply inclined to the silicate surfaces and close-packed within domains. The domains contain alternating rows of benzidine cations; from row to row the planes are either approximately parallel or perpendicular to the (120) plane, but along any one row the planes of the aromatic rings are parallel to each other. Hydrogen bonding operates between amine nitrogens and surface oxygens.
Adsorption and Catalytic Decomposition of 4-Nitrobenzenesulphonylmethylcarbamate by Smectite
Authors: Fusi Paolo , Ristori Giuseppe Gabriele , Franci Marco
Published: August 2006

Adsorption and catalytic decomposition of 4-nitrobenzenesulphonylmethylcarbamate (herbicide Nisulam) on Upton, Wyoming, bentonite saturated with different cations was studied using thin-layer chromatography and infrared spectroscopy. Nisulam is adsorbed at room temperature by coordination through the NO2 group to the exchange cation regardless of the cation's nature. On moderate heating (75°–90°C) this molecule decomposes to 4-nitrobenzenesulphonamide whereas a similar compound (herbicide Asulam) containing the NH2 functional group instead of NO2 is adsorbed by protonation at room temperature and decomposes into different products. For cations having a high polarizing power, a coordination bond between the Asulam molecule's C=O group and the exchange cation is established, and the molecule decomposes to sulphanilic and carbamic acid. In contrast, for cations having a low polarizing power there is no coordination, and the molecule decomposes mainly into sulphanilamide. Nisulam's coordination to the exchange cation through the NO2 group instead of C=O is ascribed to inductive and conjugation effects, typical of the nitro group.
Origin of Magnesium Clays from the Amargosa Desert, Nevada
Authors: Khoury Hani N. , Eberl Dennis D. , Jones Blair F.
Published: August 2006

Deposits of sepiolite, trioctahedral smectite (mixed-layer kerolite/stevensite), calcite, and dolomite, found in the Amargosa Flat and Ash Meadows areas of the Amargosa Desert were formed by precipitation from nonsaline solutions. This mode of origin is indicated by crystal growth patterns, by the low Al content for the deposits, and by the absence of volcanoclastic textures. Evidence for low salinity is found in the isotopic compositions for the minerals, in the lack of abundant soluble salts in the deposits, and in the crystal habits of the dolomite. In addition, calculations show that modern spring water in the area can precipitate sepiolite, dolomite, and calcite following only minor evaporative concentration and equilibration with atmospheric CO2. However, precipitation of mixed-layer kerolite/stevensite may require a more saline environment. Mineral precipitation probably occurred during a pluvial period in shallow lakes or swamps fed by spring water from Paleozoic carbonate aquifers.
Thin-Film Analysis of Clay Particles Using Energy Dispersive X-Ray Analysis
Authors: White G. N. , Berkheiser V. E. , Blanchard F. N. , Hallmark C. T.
Published: August 2006

A standardless method of energy dispersive X-ray fluorescence in conjunction with scanning electron microscopy was used to analyze selected areas of clay-size particles of talc, pyrophyllite, and kaolinite supported by a carbon planchet. Peak intensity ratios of fluorescing elements relative to silicon were converted directly to weight or mole ratios using conversion factors determined theoretically. The conversion factors depend upon particle thickness and mass adsorption coefficients of the sample for the elements analyzed. The effects of particle thickness become significant above ~0.1 μm. Without using particle thickness corrections, the mean molar ratios of metal to Si agreed to within 6.1,0.5, and 9.7% of the theoretical ratios for kaolinite, pyrophyllite, and talc, respectively.
A Model of Clay Swelling and Tactoid Formation
Authors: Kleijn W. B. , Oster J. D.
Published: August 2006

An electrostatic model for the stability of clay tactoids (stacks of parallel clay platelets at ~10 Å separation) in an aqueous solution has been developed. The counter ions located in the interstitial water layers are assumed to be in equilibrium with the bulk solution. Generally, the counter-ion charge density is slightly different in magnitude from the platelet charge density. Approximating the discrete charges by homogeneously charged planes, a one-dimensional potential distribution can be calculated. From this the Gibbs energy of electrostatic interaction (using single platelets as a reference) can be computed. The model predicts that clay minerals with high (vermiculite, mica) and low (pyrophyllite, talc) degrees of cationic substitution form stable tactoids. For smectites, charge density, electrolyte concentration, and counterion species determine the swelling characteristics. At a particular charge density, lower valences of the counter ions and lower electrolyte concentrations lead to increased swelling. If tactoids are formed, the number of platelets is governed by a dynamic equilibrium between electrostatic forces, van der Waals forces, and external forces, such as shear forces due to hydrodynamic flow.
The 5-M-NaOH Concentration Treatment for Iron Oxides in Soils
Authors: Kämpf Nestor , Schwertmann Udo
Published: August 2006

The boiling 5-M-NaOH treatment was found to aid in the identification and characterization of goethite and hematite by effectively concentrating the two Fe oxides in kaolinitic-gibbsitic soil clays. No transformations of goethite to hematite or hematite to goethite were detected, but poorly crystalline, highly Al-substituted goethite was found to dissolve and recrystallize into a more well-crystalline, less Al-substituted goethite in samples low in Si. The Si released from kaolinite was sufficient to block goethite dissolution and recrystallization in kaolinitic samples, but noncrystalline silica had to be added to samples rich in gibbsite to minimize this effect.
Comparison of Orientations of OH-Bonds in Layer Silicates by Diffraction Methods and Electrostatic Calculations
Authors: Bookin A. S. , Drits V. A. , Rozdestvenskaya I. V. , Semenova T. F. , Tsipursky S. I.
Published: August 2006

Orientations of OH-vectors in structural hydroxyl groups of layer silicates were defined both from diffraction data and calculations of electrostatic energy. The comparison of the results showed that for the hydroxyls of the 2:1 layers of chlorites and micas the positions of the hydroxyl protons are mainly determined by electrostatics. For the hydroxyls of dickite, amesite, and the brucitic sheets of chlorite, the results derived by the two methods differed systematically from each other, pointing to a change in the nature of the bond in these OH-groups.
Morphology of Nordstrandite
Authors: Violante P. , Violante A. , Tait J. M.
Published: August 2006

Nordstrandite was obtained synthetically by precipitation of Al(OH)3 at pH 9.0 to 11.0 in citrate or malate systems with Al: carboxylic acid molar ratios of 10–100 in the absence and in the presence of montmorillonite. Examination by transmission and scanning electron microscopy showed that the nordstrandite had a tabular morphology in the clay-free systems with Al: carboxylic acid ratio >50. Because the inhibiting effect on crystallization of the citrate or malat e anion decreases with increase in pH, the crystal size varied from <2 μm at pH 10 to 5 μm at pH 11. With increasing concentration of citrate or malate, the nordstrandite crystals became more elongated in the c-direction probably due to organic anion occupation of the coordination sites of Al on the edge faces parallel to the c-axis. Irregular growth along the c-axis was probably due to steric hindrance by the organic ligands distorting the arrangement of the unit layers of nordstrandite.

The catalytic effect of montmorillonite on the formation of nordstrandite was confirmed. Nordstrandite synthesized in the presence of montmoriUonite at pH 9.0 presented an ill-defined ovoidal outline (0.2–0.5 μm), some showing shafts of bayerite growing from the center. At higher pH, where conditions for crystalline growth were again more favorable, nordstrandite crystals nucleated on the montmorillonite surfaces and condensed in clusters of weak face-to-face associations of plates.
Intercalation of Tetraalkylammonium Cations into Smectites and Its Application to Internal Surface Area Measurements
Authors: Mercier Louis , Detellier Christian
Published: August 2006

Monolayer to bilayer (MTB) and bilayer to pseudotrimolecular (BTP) transitions were observed for smectites exchanged with symmetrical tetraalkylammonium cations of increasing sizes: +NR4, where R = (CH2)nCH3, with 0 ≤ n ≤ 7. In the case of SWy-1, SHCa-1 and SWa-1, the variation in layer spacing observed from intercalation of tetramethylammonium up to tetraoctylammonium cations showed a behavior characteristic of smectites with homogeneously distributed interlayer cations. In the case of STx-1, the change in interlayer spacing with the increase of the alkyl chain length was characteristic of a very high charge heterogeneity. Higher charge smectites (SAz-1 and SCa-3, CEC > 1.20 mmol/g) were found to have decreasing cation exchange with increasing cation size, resulting in a "leveling off’ of the interlayer spacing toward larger cations. The MTB and BTP transitions were used to determine the internal surface area of various smectites. The proposed method was found to be a quicker and simpler alternative to the polar liquid sorption method for this measurement, but was ineffective for high-charge smectites (CEC > 1.20 mmol/g).
Hydration Behavior of Na-Smectite Crystals Synthesized at High Pressure and High Temperature
Authors: Yamada Hirohisa , Nakazawa Hiromoto , Hashizume Hideo , Shimomura Shuichi , Watanabe Takashi
Published: August 2006

Hydration behavior of Na-smectite crystals synthesized at a pressure of 5.5 GPa and temperatures of 1400°–1500°C was examined by X-ray powder diffraction at various relative humidities (RH) in the range of 0–100%. The basal spacing of the Na-smectite crystal increased stepwise with increase in RH. The reflections observed were only normal reflections of a single or dual hydration states of smectite. No irrational, intermediate, or asymmetrical reflections were observed. The simple hydration behavior, not known for natural smectite with fine particle sizes and low crystallinity, indicates that the Na-smectite crystals are as perfect as common inorganic crystals with an ordered structure.
Dioctahedral Tosudite in Hydrothermally Altered Pliocene Rhyolitic Tuff, Neutla, Mexico
Authors: de Pablo-Galan Liberto , Chávez-García M. L.
Published: August 2006

Dioctahedral tosudite, a regular interstratification of dioctahedral chlorite-dioctahedral smectite, occurs associated with kaolin in the hydrothermal area of Delgado, Neutla, Mexico. Its composition corresponds to the formula:
$$\left( {S{I_{13.77}}A{L_{2.23}}} \right)A{L_8}{O_{40}}{\left( {OH} \right)_8} \cdot C{A_{0.39}}N{A_{0.03}}{K_{1.06}} \cdot \left( {A{L_{3.79}}F{E^{ + 3}}_{0.09}F{E^{ + 2}}_{0.06}M{G_{0.26}}} \right){\left( {OH} \right)_{12}}.$$ It forms as thin irregular flakes up to 5 µm in size. Adsorbed and cation hydration interlayer H2O is lost at 81°C and 184°C, dehydroxylation is intense at 496°C and weak at 656°C, with recrystallization at 970°C and 989°C. Infrared analysis shows OH-stretching at 3605 cm-1 assigned to the Al-OH-Al group and at 3628, 3500, and 3365 cm-1. Also, OH-bending occurs at 822 cm-1, deformation of the H2O molecule at 1630 cm-1, Si-O stretching at 1020 cm-1, and bending at 482 cm-1, displaced by Al substitution and increase of the Si-O distance. The characteristic basal spacing of 29.49 Å for the air-dry mineral is changed to 31.32 Å when solvated and to 23.23 Å upon heating; d060 = 1.496 Å. The interstratification is a regular 1:1 dioctahedral chlorite-dioctahedral smectite, R = 1, with coefficient of variability 0.73% for the air-dried mineral and 0.76% for the solvated one.
The Effect of Surface Modification by an Organosilane on the Electrochemical Properties of Kaolinite
Authors: Braggs Belinda , Fornasiero Daniel , Ralston John , St. Smart Roger
Published: August 2006

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.
The Effect of Dissolved Ligands on the Sorption of Cu(II) by Ca-Montmorillonite
Authors: Stadler Markus , Schindler Paul W.
Published: August 2006

The effects of three organic ligands on the adsorption of copper on Ca-montmorillonite were studied. The results indicate that these effects include three different processes:

1)

Enhanced uptake of positively charged copper-ligand complexes by ion-exchange.

2)

Formation of ternary surface complexes involving surface aluminol groups.

3)

Inhibited uptake due to competition between the surface ligands and the dissolved ligands for dissolved copper.

Ethylenediamine promotes copper uptake by ion-exchange at low pH but tends to suppress adsorption at aluminol groups by ligand competition at high pH. The same mechanisms are operative for β-alanine; however, the uptake of Cu(β-ala)+ by ion-exchange is not promoted by the attached ligand. The influence of malonate includes both ligand competition and formation of ternary complexes. A quantitative interpretation based on the surface complexation model using the least-squares programs FITEQL (Westall, 1982) and GRFIT (Ludwig, 1992) is presented. The obtained equilibrium constants are listed in Tables 2b and 3.
Interaction between Organic and Inorganic Pollutants in the Clay Interlayer
Authors: Siantar Darsa P. , Feinberg Benjamin A. , Fripiat José J.
Published: August 2006

A synergistic mechanism for the retention of organic and inorganic pollutants in clays is discussed in this paper. The mechanism of adsorption of cis- or trans- 1,2-dichloroethylene vapor (CDE or TDE, respectively) by hydrated smectite clay (hectorite) exchanged with Pb2+, Hg2+, Cd2+, Ca2+, Ag+, or Na+ has been investigated by simultaneously measuring chlorohydrocarbon uptake and water desorption isotherm and by recording the infrared (IR) spectrum of the adsorbed phase. Hydrated hectorite saturated with divalent cations adsorbs about 55% more CDE or 35% more TDE than those saturated with monovalent cations. The quantity of chlorohydrocarbon adsorbed is also a function of the hydration of the clay interlayer space. When dehydrated, hectorite does not adsorb CDE or TDE. Upon long outgassing at room temperature or even at 100°C, the characteristic IR bands of clays with adsorbed chlorohydrocarbon, although much weakened, are still observable. The ratio of the amount of water desorbed to the amount of chlorohydrocarbon adsorbed varied from about 0.22 to 0.34. A shift of the center of gravity of the hydration water OH stretching frequency towards a higher wavenumber and of the asymmetric CC1 stretching vibration toward a lower frequency suggest that the formation of hydrogen bonds between CDE or TDE and water is the driving force for adsorption and that the cation-dipole interaction does not play a major role.
Hysteresis in the Binary Exchange of Cations on 2:1 Clay Minerals: A Critical Review
Authors: Verburg Kirsten , Baveye Philippe
Published: August 2006

The binary exchange of cations on clays and soils is generally regarded as a thermodynamically reversible process. The literature on soil chemistry and geochemistry, however, abounds with reports on cation exchange reactions that appear to have only limited reversibility, i.e., that exhibit hysteresis. A satisfactory explanation of this phenomenon is still lacking, even though a number of mechanisms have been advocated, e.g., charge or site heterogeneity at the surface, differential hydration of cations, dehydration of the exchanger, crystalline swelling hysteresis, and inaccessibility of sites caused by domain or quasi-crystal formation. In the present article, the relevant literature is reviewed and analyzed critically. On the basis of available evidence, it is shown that exchangeable cations can be classified into three groups, defined in such a way that hysteresis has, in the literature, generally not been observed when exchange reactions involved cations belonging to the same group, but has often been found when the reactions involved cations from different groups. Furthermore, it is argued that none of the five mechanisms mentioned can, in and of itself, account fully for the observed exchange hysteresis. A conceptual model is proposed that combines elements of these five mechanisms and is able to describe, at least qualitatively, the effects of factors such as clay type, electrolyte concentration, and extent of dehydration.
Trimethyl Phosphate Induced Decomposition of Kaolinite
Authors: Sánchez-Camazano María , Sánchez-Martín M. Jesús
Published: August 2006

The decomposition of kaolinite by treatment with trimethyl phosphate (TMP) and the composition of the new crystalline phase formed were studied. On hot treatment with TMP, kaolinite forms a crystalline white compound that is soluble in hot water. The X-ray diffraction pattern of the kaolinite treated shows both the typical reflections of kaolinite and, furthermore, a very strong reflection at 8.84 Å. After 30 days of treatment with TMP, the silicate structure of kaolinite is completely destroyed and a crystalline phase identical with that resulting from treatment of aluminium oxide (Al2O3) with TMP is formed. The results show that the compound in question is formed by hydrolysis of TMP, catalyzed by the hydration water of exchange cations of kaolinite, followed by removal of Al from the silicate structure by incompletely hydrolyzed TMP. The new crystalline phase thus formed is an aluminium alkyl phosphate of formula Al(CH3)6(PO4)3.
Supergene Vermiculitization of Phlogopite and Biotite in Ultramafic and Mafic Rocks, Central Korea
Authors: Moon Hi-Soo , Song Yungoo , Lee S. Y.
Published: August 2006

An X-ray diffraction study of vermiculitized micas in ultramafic and mafic intrusive rocks from Cheongyang, Korea, shows the following weathering sequence: mica → ordered mica/vermiculite interstratification → vermiculite. Electron microprobe analyses show the general trends of K leaching and Ca enrichment with increased weathering. The vermiculitization of phlogopite from ultramafic rocks proceeds by means of a continuous decrease in Al-for-Si tetrahedral substitutions and a progressive increase in Al-for-(Fe2+ + Mg) octahedral substitutions in the early stage of weathering. These substitutions occur to compensate for the excess of negative charge in the mica-like layer, in agreement with currently accepted vermiculitization mechanisms. They change to a slight increase of Al-for-Si tetrahedral substitutions in the late stage of the vermiculitization of phlogopite, owing to the oxidation of Fe despite its low content. However, the behavior of Fe in the late stage of the transformation of biotite into vermiculite is significantly different; that is, Fe increases substantially. The reason for this Fe increase in the late stage remains unresolved. Recalculations of the structural formulas on the basis of several assumptions indicate that the oxidation of Fe is necessary for the vermiculite derived from biotite to form the reasonable structural formulas.
The Transformation of Lepidocrocite During Heating: A Magnetic and Spectroscopic Study
Authors: Gehring A. U. , Hofmeister A. M.
Published: August 2006

Infrared (IR) spectroscopy, in combination with magnetic methods, was used to study the thermally induced transformation of synthetic lepidocrocite (γ-FeOOH) to maghemite (γ-Fe2O3). Magnetic analyses showed that the thermal conversion began at about 175°C with the formation of superparamagnetic maghemite clusters. The overall structural transformation to ferrimagnetic γ-Fe2O3 occurred at 200°C and was complete around 300°C. At higher temperatures, the maghemite converted into hematite (α-Fe2O3). Observation of the transformation from γ-FeOOH to γ-Fe2O3 using variable-temperature IR spectroscopy indicated that dehydroxilation on a molecular level was initiated between 145°C and 155°C. The lag time between the onset of the breaking of OH bonds and the release of H2O from lepidocrocite around 175°C can be explained by diffusive processes. Overall dehydroxilation and the subsequent breakdown of the lepidocrocite structure was complete below 219°C. The comparison of the magnetic and IR data provides evidence that the dehydroxilation may precede the structural conversion to maghemite.