The 57Fe Mössbauer spectra of six nontronite samples were measured at appropriate temperatures of 4.2 and 1.3 K. Three of the nontronites gave a complex magnetic hyperfine spectrum showing magnetic ordering at 4.2 K, and the other three required a lower temperature of 1.3 K to produce similar magnetic ordering. The spectra were computer-fitted with three closely overlapping sextets which are considered to arise from: (1) Fe3+ that is ordered magnetically in the cis-octahedral sites with a greater number of neighboring tetrahedral Fe3+ ions (51 T); (2) the cis-octahedral site with the greater number of neighboring Si4+ ions (46 T); and (4) the tetrahedral sites (41 T). In an untreated sample a further sextet corresponding to interlayer Fe3+ (36 T) was identified. The magnetic ordering was complicated and not directly related to the iron content of these sites. It probably depended also on the overall composition and structural order of the particular nontronite. The ordering appears to have been essentially two-dimensional, consistent with the layer structure of this material.

A suite of Georgia kaolinites, ranging from well-ordered to very poorly ordered samples, were studied to explore correlations between degree of structural disorder, geological environment, Fe3+ content, Fe3+ electron paramagnetic resonance (EPR) spectrum, and infrared (IR) hydroxyl-stretching band frequencies and bandwidths. Samples from different localities showed a wide range of disorder which appears to be related to differences in their geological environments. High iron content correlated strongly with low degree of order. The areas of both the I and E components of the EPR spectrum and the fractional I area correlated inversely with degree of order. Fourier-transform IR studies of kaolinites and dickites showed that (1) interlayer hydrogen bonding is weaker in dickite than in kaolinite; (2) frequency of the ν11 stretching band of the inner-surface hydroxyls increases sequentially from well-ordered kaolinite through the disordered structures to well-ordered dickite, which is consistent with a model for disorder based on vacancy displacement; and (3) the character and temperature dependence of the inner hydroxyl-stretching band is not compatible with the crystal structures of kaolinite and dickite as refined by Suitch and Young.

Mixtures of synthetic Al-substituted goethite (α-Fe0.814Al0.186OOH) and hematite (α-Fe1.658Al0.342O3) (75, 50, 25, 3% hematite by weight) were studied by Mössbauer spectroscopy to evaluate the use of that technique for quantitative analysis. Mössbauer spectra for these mixtures, obtained in the temperature range 12–130 K, were better fitted by a distribution of magnetic fields than by two magnetic sextets. Spectra at 80 K were equally as good as those from lower temperature to determine the hematitegoethite ratio. The recoil-free fractions of the individual components were about equal at any fixed temperature, but thickness effects caused as much as 30% error in the determination of the ratio of components in mixtures.

The Rokle bentonite deposit is part of an accumulation of argillized volcanoclastic rocks in the Tertiary stratovolcanic complex of the Doupovské Mountains east of Karlovy Vary (Carlsbad), about 100 km westnorthwest of Prague, Czechoslovakia. The arenite basalt ash was originally composed of hyaloclasts and subordinate biotite. The following types of montmorillonite aggregates were produced during the alteration of the ash in a stagnant, lacustrine environment: (1) extremely fine-grained micro-crystalline aggregates that have honeycomb textures and that replace the original hyaloclasts, and (2) coarse crystalline aggregates that have more open honeycomb textures and that fill pores and cracks in altered hyaloclasts and in pumice vesicles. Both types of aggregates have the same chemical composition according to energy dispersive X-ray analysis.

Montmorillonite, separated as the <1-¼m size fraction from olive gray bentonite, has the following crystallochemical formula: (K0.09Na0.02Ca0.29Mg0.10) (Al2.43Fe3+1.05Fe2+0.005Mn2+0.005Mg0.50) (Si7.62Al0.38) O20(OH)4. Biotite was apparently stable during the alteration of the hyaloclasts. Anatase and possible accessory heulandite-clinoptilolite were also formed in small amounts, but were not observed by scanning electron microscopy. Goethite is the youngest oxidation product in some parts of the bentonite. Minute fragments of sodium-rich plagioclase, potassium feldspar, quartz, and muscovite are ubiquitous accessories of the original hyaloclasts. Together with kaolinite, they formed from the underlying fresh or kaolinized orthogneiss.

An ochreous precipitate isolated from a stream receiving acid-sulfate mine drainage was found to consist primarily of goethite and lesser amounts of ferrihydrite-like materials. The Fe-oxide fraction, including goethite, was almost totally soluble in acid ammonium oxalate. Similar materials were produced in the laboratory by hydrolysis of ferric nitrate solutions containing 250 to 2000 μg/ml sulfate as Na2SO4. Initial precipitates of natrojarosite transformed to Fe-oxides upon aging for 30 days at pH 6.0. The proportion of goethite in the final products decreased with increasing sulfate (SO4/Fe = 0.2 to 1.8) in the initial hydrolysis solutions; only ferrihydrite-like materials were produced at SO4/Fe ratios > 1.5. Variations in SO4/Fe solution ratios also produced systematic changes in the color (10R to 7.5YR) and surface areas (49 to 310 m2/g) of the dried precipitates, even though total S contents were relatively constant at 2.5 to 4.0%.

As part of the characterization of a Tunisian red soil profile, six samples, taken at different depths, were investigated by Mössbauer spectroscopy at room temperature and at 80 K to obtain information about the various types of Fe oxides present. By considering magnetic hyperfine field distributions, the spectra of goethite and hematite were well resolved. Chemical analyses of the samples revealed a partial substitution of Fe by Al and Mn. The spectral behavior of the goethite was predominantly influenced by crystallinity and amount of Al substitution which resulted in a reduction of the magnetic hyperfine field. The effect of Mn substitution was much more pronounced in the hematite spectrum as a consequence of a stronger suppression of the Morin transition by Mn than by Al.

The dehydration temperature of K-montmorillonite, obtained by ion exchange of a Na-mont-morillonite, was determined at pressures to 2 kbar, using high-pressure differential thermal analysis. Dehydration reactions were found at about 50° and 100°C above the liquid-vapor curve of water. At pressures above the critical point of water the dehydration temperatures increased only slightly. The temperature of the first dehydration reaction is 10°C higher than for Na-montmorillonite, indicating a slightly greater stability of the hydration shell around the potassium interlayer cation. The second dehydration reaction occurs at a slightly lower temperature. The data were used to determine the enthalpy of the dehydration ΔH(dh) and the bonding enthalpy of the interlayer water ΔH(iw) at 1 atm. The first dehydration reaction of the K-exchanged montmorillonite has a ΔH(dh) = 46.16 ± 0.06 kJ/mole and a ΔH(iw) = 7.8 ± 0.5 kJ/mole, whereas for the second reaction, ΔH(dh) = 56.7 ± 2 kJ/mole and ΔH(iw) = 19.8 ± 2 kJ/mole. These values compare with a ΔH(dh) = 46.8 ± 0.3 kJ/mole and a ΔH(iw) = 7.8 ± 0.5 kJ/mole for the first dehydration reaction of the Na-montmorillonite and a ΔH(dh) = 62.9 ± 2 kJ/mole and ΔH(iw) = 27.1 ± 2 kJ/mole for the second dehydration.

The reactions of simple conjugated dienes over divalent and trivalent transition metal-exchanged montmorillonites yield, in the absence of nucleophiles, a variety of products. Some of these products are a result of Diels-Alder cycloaddition reactions, whereas others are indicative of carbocation intermediates, i.e., other dimers, oligomers, and isomerization products of these intermediates. The reactions in sealed cells between 20° and 150°C show trends in the yields of the various product groups. Dimers of butadiene and isoprene formed by cycloaddition (i.e., 4-vinylcyclohexene and the monoterpene p-menthadiene (limonene)) were formed at low temperatures (20–50°C). As the temperature was raised, the total yield of dimers increased and higher oligomers were formed along with isomerization products of the dimers and oligomers. The products of cycloaddition, however, did not increase markedly. The type of solvent used for the reaction was found to influence the reactivity, e.g., the use of 1,4-dioxan rather than chloroform led to a reduction in total conversion and also to a markedly higher degree of selectivity. In the presence of a suitable nucleophile (methanol), both dienes gave the 1,4-addition product predominantly, which suggests that an allylic carbocation intermediate was involved. The use of an interlayer-supported nickel complex, [HNi(P(OEt)3)4]+, produced the only large scale polymerization observed in this work.

Batch data for the sorption of Eu and Th on pelagic sediments may be represented by equations of the form: ln M = A ln Cs + B/T + D, where M = concentration of sorbate on sediment, Cs = concentration of sorbate in solution, T = absolute temperature, and A, B, and D = constants. Thermodynamic interpretation of this equation leads to an expression for the true thermodynamic equilibrium constant of K = m/CsA and for the enthalpy change, ΔH, of d ln(M/CsA)/d(1/T) = −ΔH/R, where R = universal gas constant.

Experimentally, the sorption of Eu onto clay-rich sediments was very rapid in the first few seconds and slowed over an interval of minutes to hours. Rate curves were similar in shape to those of α-iron hydroxide, rather than of the oxalate-extracted residual sediment, indicating the importance of oxyhydroxide-like phases in the uptake of Eu onto red-clay sediments. For clay-rich sediments, numerical modeling reproduced the general features of a series of diffusion experiments. To a first approximation, the penetration of Eu into a sediment proceeded by saturation of the sediment to the depth of penetration and produced a sharp drop-off in sorbed + dissolved Eu concentration at the diffusion front. Higher partition coefficients (Kp) resulted in greater sorbed + dissolved concentrations, but reduced penetration. For calcareous sediments, however, Eu concentrations at the surface were much higher than at depth, presumably due to the formation of an insoluble carbonate.

The 57Fe Mössbauer spectra of several montmorillonites, measured at room temperature and 453 K, showed a considerably broadened Fe3+ resonance which can be computer-fitted with a similarly broadened Fe3+ doublet. In some spectra, particularly if all linewidths were constrained to be equal, this broadened Fe3+ resonance was further resolved into overlapping inner and outer Fe3+ doublets, also having broad linewidths. In accordance with recent electron diffraction evidence, the assignment by previous workers of the inner doublet to Fe3+ in the octahedral sites having the cis-arrangement of OH groups and the outer doublet to the octahedral site having the trans-arrangement of OH groups is incorrect. Instead, the Fe3+ was found to be located largely in the trans-octahedral sites. Because of the relatively low iron content of the montmorillonite examined, the next and more distant neighboring-cation environment varied considerably about the octahedral Fe3+ ions. This variation produced a broadened experimental resonance, and the resulting two-doublet computer fits probably represent the mean extremes of a continuum of slightly different Fe3+ resonances arising from the variable nature of the environment surrounding these such trans-sites, rather than distinct cis- and trans-sites. In addition, a small resonance indicating the substitution of Fe3+ into the tetrahedral sites was observed. The interlayer species probably influenced the Mössbauer resonance of Fe3+ in the tetrahedral and octahedral sites.

Three post-glacial marine clays from eastern Canada and one marine clay from Japan have been studied by Mössbauer spectroscopy to ascertain their iron mineralogy. Small amounts of hematite (in two samples) and magnetite (in one sample) were found in the Canadian clays, and hematite was detected in the Japanese clay. The major spectral components were ferrous and ferric doublets, consistent with X-ray powder diffraction results that show chlorite, mica, and amphibole in the Canadian samples and smectite in the Japanese sample. Citrate-dithionite extraction removed hematite and most of the magnetite from these samples. Acid-base extraction also removed chlorite and some mica from the Canadian samples. Samples treated by these extractions had appreciably lower geotechnical yield stresses at given water contents.

X-ray powder diffraction patterns for many interstratified kaolinite/glycolated smectites were calculated by changing combinations of probabilities and transition probabilities of two component layers. Reichweite = 0 and Reichweite = 1 structures were investigated. The calculated d-values were plotted, with PKS (the probability that a smectite layer succeeds a kaolin layer given that the first layer is a kaolinite layer) and PSK as the axes of coordinates. These d-values were then linked into equal d-value curves on a graph. Four equal d-value diagrams for mixed reflections ranging from 34.0 to 17.1 Å, from 8.5 to 7.2 Å, from 6.13 to 5.68 Å, and from 3.540 to 3.401 Å were constructed. Two examples of identifying natural kaolinite/smectite minerals using these diagrams are presented.

The approximate maximum and minimum amounts of any phase in a complex mineral mixture can be determined by solving a linear programming problem involving chemical mass balance and X-ray powder diffraction (XRD) data. The chemical information necessary is the bulk composition of the mixture and an estimation of the compositional range of each of the minerals in the mixture. Stoichiometric constraints for the minerals may be used to reduce their compositional variation. If only a partial chemical analysis for the mixture is available, the maximum amounts of the phases may still be estimated; however, some or all of the stoichiometric constraints may not apply. XRD measurements (scaled using an internal standard) may be incorporated into the linear programming problem using concentration-intensity relations between pairs of minerals. Each XRD constraint added to the linear programming problem, in general, reduces the difference between the calculated maximum and minimum amounts of each phase. Because it is necessary to define weights in the objective function of the linear programming problem, the proposed method must be considered a model. For many mixtures, however, the solution is relatively insensitive to the objective function weights.

An example consisting of a mixture of montmorillonite, plagioclase feldspar, quartz, and opal-cristobalite illustrates the linear programming approach. Chemical information alone was used to estimate the mineral abundances. Because quartz and opal-cristobalite are not chemically distinct, it was only possible to determine the sum, quartz + opal-cristobalite, present in the mixture.

Weathering of a copper stratiform deposit (schist) at Salobo, Brazil, has produced two distinct Cu-bearing minerals from a biotite parent: vermiculite and a manganese oxide containing as much as 13% and 25% CuO, respectively. Manganiferous products were formed as the result of an interhorizon transfer of solutions through a fissure system. Thus, the structural orientation of the schists was a major factor in controlling the supergene concentration of Cu. The Cu-vermiculite formed by the weathering of Fe-biotite, although the unweathered biotites in the parent rocks were found to contain no copper, suggesting that Cu was supplied by weathering solutions. X-ray powder diffraction (XRD) and cationexchange capacity data for the Cu-vermiculite differ from those of typical Mg-vermiculite and are similar to those of hydroxy- Al-vermiculite. A comparison of the XRD pattern of the Cu-vermiculite with that of a Cu-free vermiculite indicates that Cu atoms are located in interlayer sites. Cu probably occurs in a brucite-like layer. The position and structure of the Cu K-absorption spectrum suggest that the Cu is divalent and exists in 6-fold coordination.

A method using Li saturation and heating to 250°C to differentiate montmorillonite from beidellite and nontronite has been developed. The test utilizes three washings with 3 M LiCl and two washings with 0.01 M LiCl in 90% methanol to prevent dispersion. An 'infinitely thick’ sample (6–8 mg/cm2) on a glass slide is used to avoid the effects of the reaction of a thin clay film with sodium of the slide when it is heated at 250°C. Solvation with glycerol rather than ethylene glycol is used, because all of the Li smectites studied expanded to some extent in ethylene glycol after the heating. The smectites included several montmorillonites, a nontronite, and saponites. The presence of interstratified montmorillonite and beidellite layers was clearly shown by the test for several smectite samples, including the so-called beidellites from Beidell, Colorado, and Chen-yuan, Taiwan, and several soil clays. The test thereby provides more mineralogical information than the often-used arbitrary dividing point between montmorillonite and beidellite at 50% tetrahedral charge. Heating the Li-saturated clays at 250°C caused substitution of 35 to 125 meq/100 g of nonexchangeable Li. These amounts exceeded the changes in cation-exchange capacity plus Li by 4 to 21 meq/100 g, except for the end-member beidellite from the Black Jack mine, Idaho. Fusion with LiNO3 at 300°C could not be used to differentiate between smectites instead of washing with LiCl solution and heating to 250°C, because fused montmorillonite subsequently expanded to 18 Å with glycerol. Large increases in nonexchangeable Li were caused by the fusion of smectites, a vermiculite, and two partially expanded micas.