A correlation was made of crystallochemical data from 15 smectites with the half time of dissolution (t05) in 6 N hydrochloric acid at 96°C. From this the relation

ln t05 = 3.95 - 1.96 FeVI - 2.30 MgVI

was developed. It shows a remarkable dependence of the apparent dissolution rate of the octahedral layer of the smectites on the substitution of Fe3+ and Mg2+ for Al+3 in the octahedral position.

The low temperature synthesis of iron silicate minerals with clay structures is possible at surface temperatures only under reducing conditions. Under oxidizing conditions clay minerals could not be synthesized. Instead quartz and quartzine were found in these X-ray amorphous Fe III hydroxide-silica precipitates after 14 days at low temperatures (20° and 3°C) as well as geothite or X-ray amorphous iron hydroxides. Only from solutions containing Fe-II could the different iron-containing clay minerals be built up within days at low temperatures. The presence of Fe-II enables an octahedral layer of the brucite-gibbsite type to be formed. This is necessary for the bidimensional orientation of SiO4-tetrahedra leading to clay mineral formation. The presence of Fe2+- and/or Mg2+-ions is necessary for the formation of the Al3+- and Fe3+-containing octahedral layers. The reducing conditions were obtained in the experiments by addition of dithionite. With a high content of silica (ca. 20 ppm SiO2,7 ppm Fe) nontronite and lembergite, the di-Fe-III and tri-Fe-II octahedral, three-layer silicates, were built up in several days at low temperatures. With a lower silica content, that is, a lower Si/Fe ratio (15 ppm SiO2 and 20 ppm Fe), the two-layer silicate minerals greenalite and chamosite could be synthesized. A higher Mg content and more reducing conditions in the solutions favored the tri- as well as dioctahedral chamosite synthesis.

The conditions of formation of recent naturally formed nontronite fit well with the synthesis conditions. Chamosites in sedimentary iron ores are characterized by a low content of SiO2, between 15–30% SiO2. This low content of silica cannot be the result of primary precipitation from seawater. The iron and silica ratio in seawater or in river waters would lead to a precipitation of ~60% SiO2 in the iron hydroxide precipitates. A probable origin for chamosite iron ores, which explains the low SiO2 content, is diagenesis of the lateritic weathering crust. Indeed, investigations of recent tropical shoreline sediments and in particular their trace element content confirm that chamosite minerals have formed diagenetically from lateritic particles in reducing sediments.

Infrared and Mössbauer spectroscopy show that the extent of the reduction of nontronite is dependent on the chemical composition of the nontronite and on the nature of the reducing agent. Hydrazine reversibly reduces about 10% of the iron in all of the nontronites studied irrespective of composition and it is suggested that the resulting ferrous iron occurs only in distorted octahedral sites. Similar conclusions are reached for the dithionite reduction of the nontronites containing little tetrahedral iron, but for those with more than one in eight silicons replaced by iron, changes brought about by dithionite treatment are irreversible due to dissolution of appreciable quantities of iron. Results from both spectroscopic techniques suggest that iron in tetrahedral sites is preferentially dissolved and that up to 80% of the structural iron can be reduced.

Evidence is presented for the formation in these extensively reduced nontronites of a small amount of a mica-like phase resembling celadonite or glauconite, and, as dithionite is used for the pretreatment of soils, the implication of this observation is briefly discussed.

The use of deuterated hydrazine as a reducing agent has enabled the nontronite absorption band near 850 cm-1 to be assigned to a Si-O (apical) stretching vibration, which is inactive in the infrared for perfect hexagonal symmetry, but which is activated by distortions in the tetrahedral layer.

Using Garfield, Washington, nontronite as the model mineral system, methods and apparatus were developed to prepare reduced suspensions in citrate-bicarbonate-dithionite (CBD) solution. These techniques were effective in removing excess, undesired solutes from reduced suspensions while maintaining a high Fe2+ content. They also enabled the preparation of dried, reduced films preferentially oriented with respect to the crystallographic c-axis. Supernatant solutions were collected and analyzed for Fe, Al, and Si, from which the extent of dissolution of the clay as a result of CBD treatment was assessed. Results indicated that very little Fe and Si were released to solution, but as much as about 8% of the total Al was solubilized. The highest levels of Al in solution were observed in CB treatments without dithionite.

To understand the genetic relationship between hisingerite material in the joints of an overlying grey basalt and nontronite and Fe-rich saponite in the joints and matrix of a more deuterically altered, underlying green basalt, the hisingerite material was treated in a series of hydrothermal experiments. No well-ordered clay mineral was produced at temperatures <340°C, although extended treatment for 445 days and at 110°C or 42 days at 180°C resulted in the formation of materials that gave broad, weak, basal X-ray powder diffraction (XRD) reflections characteristic of 2:1 phyllosilicates. Hematite did not form at 110°C, but it did form at 180°C in 1- and 6-week runs. Treatments at 340°C in Pt, Ag-Pd, and Au containers resulted in mixtures of Fe-rich saponite + hematite, but the same starting material treated at 340°C in stainless steel yielded, in addition, some chlorite, probably due to the more reducing conditions in the stainless steel container. Treatment of the unaltered grey basalt at 340°C and 50 MPa for 10 days resulted in complete alteration of olivine (and probably glass) to a trioctahedral smectite.

The Fe-rich saponite produced by the hydrothermal treatment of the hisingerite material has a composition and XRD pattern similar to the Fe-rich saponite found in the green basalt and an XRD pattern similar to that produced by the hydrothermal treatment of the grey basalt; thus these clays may have had a similar origin. The compositions and XRD patterns of these clays are not similar, however, to those of the nontronite in the joints of the green basalt. The nontronite probably formed during a subsequent low-temperature alteration.

The effects of reduction and reoxidation of octahedral Fe3+ on the exchange of structural hydrogen in nontronite were determined using tritium (3H) as a label element. The uptake of H from the surrounding solution of nontronite suspensions increased as the reduction of structural Fe3+ increased. Similarly, the loss of H from the structure increased as the reduction increased. The results are generally consistent with a reduction mechanism involving the loss of structural OH, leaving the affected Fe sites with less than six-fold coordination. The attenuation of increased negative charge on the clay layer, however, was less than predicted by such a mechanism.

During the reoxidation of reduced nontronite in suspension, about one-third of the H remaining as part of the structure following reduction was lost, whereas twice that amount of H was incorporated into the structure from the surrounding solution. A reoxidation mechanism is proposed whereby H2O from the surrounding solution is incorporated into the mineral structure followed by the elimination of a hydrogen ion, returning the Fe to six-fold coordination. This mechanism implies the reversibility of Fe reduction in nontronite.

The 57Fe Mössbauer spectra of a series of untreated and Ca-saturated nontronites showed a predominant Fe3+ resonance which was computer-fitted with two Fe3+ doublets defining iron in non-equivalent cis-FeO4(OH)2 octahedral sites. In most spectra a doublet indicating tetrahedral Fe3+ was fitted and in one untreated sample a doublet indicating interlayer Fe3+ was identified. In a further untreated sample the interlayer iron was present as Fe2+. Upon Ca-saturation the interlayer iron was displaced. It also appears that the interlayer iron was present in at least two different interlayer sites. From the computer-fitted data it was clear that the interlayer cations have a significant effect on the Mössbauer resonances of iron in the two non-equivalent cis-octahedral and the tetrahedral sites of nontronite.

Dehydration-induced migration of different exchangeable cations toward the layers of nontronite has been studied by Mössbauer spectroscopy. As interlayer water is removed exchangeable cations migrate toward Fe3+ sites in the tetrahedral sheets of the nontronite (IvFe3+) causing them to distort. The amount of distortion is linearly related to the ionic potential (IP) of the exchangeable cations and is greatest for cations with highest IP. Octahedral Fe3+ sites (VIFe3+) are also affected by migration of cations into the pseudohexagonal cavities. As exchangeable cations move into the pseudohexagonal cavities, interaction with VIFe3+ sites increases. The intensity of the outer VIFe3+ Mössbauer doublet increases with respect to the inner VIFe3+ doublet as the IP of the exchangeable cation increases. It appears that the exchangeable cations play a significant role in determining the thermal stability of nontronite.

In Upper Cretaceous-Tertiary marine shales (Campos Formation) from the Campos basin, Brazil, mixed-layer illite/smectite (I/S) has remained randomly interstratified to depths of 3500 m and to temperatures as high as 100°C, in contrast to the typical pattern of shale diagenesis in, for example, the Gulf Coast area. X-ray powder diffraction analysis of the bulk shale and several size fractions from samples from one well in the Brazilian basin and from one in the Gulf Coast region were carried out to assess the factors that might have controlled the lack of illitization in the Campos Formation shales.

In samples from the Gulf Coast well, the clay minerals are I/S (montmorillonite-type), discrete illite, chlorite, and minor kaolinite. In contrast, the clay minerals in samples from the Campos basin well are kaolinite, clay-size biotite, and I/S (nontronite-type). Kaolinite is abundant in this well, and the variation of its abundance with depth seems to reflect variations in sea-level stands. The original composition of the I/S (nontronite-type) was probably the main factor controlling the lack of illitization in the shales of the Campos Formation.

The catalytic power of Ca-nontronite (0.2–2 μm) for the polycondensation of phenols and glycine and the associated reactions that involve the ring cleavage of phenols and the decarboxylation and deamination of glycine was studied in systems free of microbial activity. At the end of a 90-hr reaction period, the amount of CO2 released from the Ca-nontronite-glycine-pyrogallol, Ca-nontronite-glycine-eatechol, and Ca-nontronite-glycine-hydroquinone systems were 5.1, 8.7, and 11.6 times higher, respectively, than those from the respective nontronite-free systems, showing the catalytic role of Ca-nontronite in the ring cleavage of phenols and the decarboxylation of glycine. The release of CO2 and NH3 from the Ca-nontronite-glycine system revealed that Ca-nontronite can catalyze decarboxylation and deamination of glycine. The ability of Ca-nontronite to catalyze the deamination of glycine was substantially enhanced by the presence of a phenol. The visible absorbances at both 472 and 664 nm of the supernatants, the total yields of N-containing humic polymers, and the fractions of glycine converted to nitrogenous polymers indicated that polycondensation of glycine and phenol was greatly catalyzed by Ca-nontronite. The total N-containing humic polymers formed in the systems decreased in the order: Ca-nontronite-glycine-pyrogallol > Ca-nontronite-glycine-cateehol > Ca-nontronite-glycine-hydroquinone > glycine-pyrogallol > glycine-hydroquinone > glycine-catechol. The infrared and electron spin resonance spectra of humic acid (HA) and fulvic acid (FA) formed in the supernatants of the reaction systems were quite similar to those of soil HA and FA. The catalytic power of Ca-nontronite in affecting the ring cleavage of phenols, deamination and decarboxylation of amino acids, and formation of humic substances derived from phenols with amino acids in soils and the related environments thus merits attention.

Smectite close to the pure Fe end member of the nontronite-beidellite series was found in the fine clay separated from a 354-cm deep sediment core in the southwestern Pacific Basin. The mineral has a b-axis of 9.09 Å and an unusually low dehydroxylation temperature of 454°C and is composed of sheaves of fibers less than 50 Å wide. Its charge density is 5.09 × 10~4 esu/cm2. The charge originates mainly from the presence of 18% of the total Fe in tetrahedral positions, as determined by Mössbauer analysis. Slight deviations of the infrared spectra from those reported for nontronites are probably due to the presence of more octahedral Mg. The presence of authigenic quartz in the same sample permits some speculation on the concentration of dissolved silicon during nontronite genesis. A δ18O value of 26 ± 0.3‰ indicates a temperature of formation of about 22°C. The Sr isotope ratio suggests that the nontronite formed at least 12 million years ago.

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.

Iron impurities in the Hohen Hagen nontronite (NG-1) were identified as maghemite and goethite. The phase identified as maghemite was magnetically ordered at both room temperature and 87 K, with hyperfine magnetic fields of 48.6 and 50.7 tesla, respectively. Due to the magnetic properties of this phase, it was easily separated from aqueous dispersions of the clay using a hand magnet. X-ray powder diffraction analysis revealed maghemite, quartz, and phyllosilicate in the magnetically separated phase. The impurity identified as goethite remained in the non-magnetic <2-μm fraction of the clay, displayed magnetic order only at 87 K (47.44 tesla hyperfine field), and accounted for about 8% of the total area of the Mössbauer spectrum.

The effect of Fe oxidation state on the specific surface area, Sm, of nontronite was studied using the <2-µm, Na+-saturated fraction of the SWa-1 and Garfield nontronite reference clays. The reduction of structural Fe3+ in the octahedral sheet of the nontronite decreased Sm as measured by the adsorption of 2-ethoxyethanol (ethylene glycol-monoethyl ether, EGME). The swellability in water of the nontronite also decreased during reduction. The amount of nonexchangeable Na+, on the other hand, increased with increasing Fe2+ content and was highly correlated with EGME adsorption (r = -.985). The relationship between Sm and Fe2+ was attributed to the collapse of partially or fully expanded layers to unexpanded layers.

A new type of environmental chamber for X-ray diffraction was designed that could sustain elevated, internal pressures of nitrogen or any other gas under oxygen-free conditions and that allowed the positions of the specimen and edge aperture to be adjusted by remote control. It was used to determine the values of the interlayer spacing, λ, of nontronite from Garfield, Washington, in different stages of reduction at different values of Π, the swelling pressure of the nontronite. At equilibrium, Π was equal to the pressure under which water was expressed from the clay. Both partially and fully expanded layers were found to exist in the reduced nontronite, the fraction of partially expanded layers increasing with increasing Π and Fe2+/Fe3+, the ratio of Fe2+ to Fe3+ in octahedral sites. Also, λ for the partially expanded layers was found to depend on Fe2+/Fe3+ but not on Π, and λ for the fully expanded layers was found to depend on Π but not on Fe2+/Fe3+. These findings were interpreted to mean that the reduction of Fe affected the short-range interlayer forces, but not the long-range ones.