The rapid phase quantification method using X-ray diffraction (XRD) with a position-sensitive detector (PSD), outlined by Cressey and Schofield (1996), has been extended to facilitate mineral phase quantification of clay-bearing samples. In addition, correction factors for differences in matrix absorption effects have been calculated and applied. The method now enables mudrock mineralogy to be quantified rapidly and efficiently. Using this approach overcomes many of the problems hitherto associated with the quantitative analysis of clay minerals, in particular the effects of preferred orientation of crystallites and variable sample-area irradiation, that make the task of quantification extremely difficult by conventional Bragg-Brentano scanning diffractometry.

Hectorite and saponite are exchanged with [Al13O4(OH)24(H2O)12]7+ and the amount of Al3+ adsorbed and Na+ released are followed as a function of the exchange conditions. On saponite the reaction is a pure ion exchange with 2–2.15 mmol Al3+/g adsorbed and release of 0.80 mmol Na+/g. On hectorite the ion exchange is accompanied by supplementary hydrolysis-polymerization of Al13. When excess Al is offered in the form of Al13, ion exchange is incomplete and is accompanied by precipitation and polymerization of Al13 on the surface of both hectorite and saponite. The typical spacing of 1.8 nm is developed after washing, when at least 1.3–1.4 mmol Al3+/g is adsorbed. Above a loading of 2.2–2.5 mmol/g the 1.8 nm spacing is obtained without washing. Only pillared saponite with a loading of at least 1.9 mmol Al3+/g is thermally stable up to 550°C.

Batch reactor experiments were performed at 150°C, 175°C, and 200°C to determine the effect of high pH NaOH solutions on the mineralogy of the Opalinus shale. In these experiments, the change in solution quench pH at 25°C, solution composition, and mineralogy were monitored as a function of time for up to ≈40 days. Runs were performed in 50 ml titanium hydrothermal reactor vessels. Each reactor was charged with 0.5–5.0 g of the 80–200 mesh size fraction of Opalinus shale, and 25 ml of solution (0.1 and 0.01 M NaOH). The general sequence of reaction products observed under these high pH conditions include first the formation of analcime, followed by vermiculite, and finally Na-rectorite formation.

The compound Mg2+-Al3+-(Fe(CN)6)4−, with a structure similar to hydrotalcite Mg6Al2(OH)16CO3 ·4H2O, is prepared by a coprecipitation method. Chemical, thermal, and X-ray analysis of the compound lead to the formula: $(M{g}_{0.741}A{l}_{0.259}(OH{)}_2)((F{e}^{II}(CN{)}_6{)}_{0.067}(C{O}_3{)}_{0.002}(H_{2}O{)}_{1.05})$

The compound is dehydrated at 100° to 250°C, and the adsorption of N2, O2, CO2, and H2 on it is measured at −196°C to room temperature by the volumetric method. The water is removed reversibly from 100° to 200°C, and the interstices after dehyration act as sites of adsorption. When dehydration is carried out at 150°C, the adsorptive activity reaches a maximum. Adsorption isotherms of N2 and O2 at −196°C and of CO2 at room temperature are of the Langmuir type, and the saturated amounts of N2, O2, and CO2 adsorbed are 96.3, 65.2, and 91.8 ml (STP)/g, respectively.

Adsorption isotherms of N2 and O2 at room temperature are of the Henry type. The amount of O2 adsorbed is about 67% of that of N2. The isosteric heats of adsorption at room temperature of N2, O2, and CO2 are 5.1, 4.8, and 11.0 kcal/mol, respectively. A dehydrated product of a Mg2+-Al3+-CO32− compound does not permit adsorption of CO2 at room temperature, but permits the adsorption of H2O. Hence, it has a molecular sieve effect. No adsorption of H2 is observed in any of the compounds tested.

The hot spring water discharging from a flank of an active volcano is precipitating unique monomineralic manganese deposits over volcanic terrain. The major and trace element chemistry, XRD mineralogy, DTA, and SEM observations indicate that the deposits consist of 10 Å phyllomanganate (buserite) accommodating inter-layer Ca and Mg with negligible amounts of detrital minerals. Other metallic elements can be accommodated by buserite, but concentrations are negligible ranging less than 10 ppm to 500 ppm. Abundance and pattern of REE (less than 100 ppm in total) are similar to those from hydrothermal manganese deposits. The buserite is enriched in Ca and Mg but depleted in Na in comparison with those in the spring water. The distribution coefficients for Ca, Mg and Na between the buserite and the host water were calculated assuming an ion-exchange equilibrium in the Yuno-Taki Fails, which proved applicable to other manganese deposits from surficial environments on land and oceans.

In deep geological repositories for high-level nuclear wastes, interactions between steel canisters and clay-rich materials may lead to mineralogical transformations with a loss of the confining properties of the clays. Experiments simulating the conversion of smectite to Fe-rich clay phases in contact with Fe metal have been carried out to evaluate such a possibility by taking into account the effects of a series of critical parameters, including temperature, pH, and Fe/clay (Fe/C) and liquid/clay (L/C) ratios. The mineralogical and chemical transformations observed in these experiments have been compared with data from the literature, and subsequently used to propose a conceptual model for the main mineralogical transformations which can be expected in clay formations surrounding high-level nuclear waste repositories. In the presence of Fe metal and under low oxygen fugacity (<-40) the main mineralogical sequences are as follows:

1. (1) up to 150°C, under neutral pH, and L/C > 5: dioctahedral smectite (di-sm) → 7 Å Fe-rich phase (berthierine, odinite-cronstedtite) for large Fe/C ratios (>0.5), or di-sm → Fe-rich di-sm + Fe-rich trioctahedral smectite (tri-sm) for small Fe/C ratios (0.1)

2. (2) up to 150°C, under alkaline pH (10–12), and L/C > 5: di-sm → Fe di-sm (±palygorskite) for a small Fe/C ratio (0.1)

3. (3) at 300°C, Fe/C = 0.1, and L/C > 5: di-sm → Fe-rich saponite → trioctahedral chlorite + feldspar + zeolite (near-neutral pH); di-sm → Fe-rich vermiculite + mordenite (pH 10–12).

Low temperatures (<150°C) and large L/C and Fe/C ratios seem to favor the crystallization of the serpentine group minerals instead of Fe-rich trioctahedral smectites or chlorites, the latter being favored by higher temperatures. The role of L/C and Fe/C ratios and the competition between them at different temperatures is a crucial point in understanding the transformation of smectite in contact with Fe metal.

Amorphous derivates prepared by aqueous reaction of various aluminosilicate clay minerals with concentrated KF solution at 80–110°C were studied for their gas adsorption properties. The four clay minerals studied are halloysite, a well-crystallized kaolinite, a poorly crystallized kaolinite, and a montmorillonite. The gases tested are N2, O2, CH4, CO, CO2, and C2H2. The kaolin-group mineral derivatives are characterized by substantial reduction in particle size, high specific surface, and significant selectivity towards CO2 and C2H2 relative to the other gases. The montmorillonite derivative shows no increase in adsorption over the starting material, however, for all the materials high adsorption of CO2 and C2H2 was observed. Levels of gas adsorption and gas adsorption ratios are comparable to pillared clays.

The reduction of structural Fe in smectite is mediated either abiotically, by reaction with dithionite, or biotically, by Fe-reducing bacteria. The effects of abiotic reduction on clay-surface chemistry are much better known than the effects of biotic reduction. Since bacteria are probably the principal agent for mediating redox processes in natural soils and sediments, further study is needed to ascertain the differences between biotic and abiotic reduction processes. The purpose of the present study was to compare the effects of dithionite (abiotic) and bacteria (biotic) reduction of structural Fe in smectites on the clay structure as observed by infrared spectroscopy. Three reference smectites, namely, Garfield nontronite, ferruginous smectite (SWa-1), and Upton, Wyoming, montmorillonite, were reduced to similar levels by either Shewanella oneidensis or by pH-buffered sodium dithionite. Each sample was then analyzed by Fourier transform infrared spectroscopy (FTIR). Parallel samples were reoxidized by bubbling O2 gas through the reduced suspension at room temperature prior to FTIR analysis. Redox states were quantified by chemical analysis, using 1, 10-phenanthroline. The reduction level achieved by dithionite was controlled to approximate that of the bacterial reduction treatment so that valid comparisons could be made between the two treatments. Bacterial reduction was achieved by incubating the Na-saturated smectites with S. oneidensis strain MR-1 in a minimal medium including 20 mM lactate. After redox treatment, the clay was washed four times with deoxygenated 5 mM NaCl. The sample was then prepared either as a self-supporting film for OH-stretching and deformation bands or as a deposit on ZnSe windows for Si-O stretching bands and placed inside a controlled atmosphere cell also fitted with ZnSe windows. The spectra from bacteria-treated samples were compared with dithionite-treated samples having a similar Fe(II) content. The changes observed in all three spectral regions (OH stretching, M2-O-H deformation, and Si-O stretching) for bacteria-reduced smectite were similar to results obtained at a comparable level of reduction by dithionite. In general, the shift of the structural OH vibration and the Si-O vibration, and the loss of intensity of OH groups, indicate that the bonding and/or symmetry properties in the octahedral and tetrahedral sheets changes as Fe(III) reduces to Fe(II). Upon reoxidation, peak positions and intensities of the reduced smectites were largely restored to the unaltered condition with some minor exceptions. These observations are interpreted to mean that bacterial reduction of Fe modifies the crystal structures of Fe-bearing smectites, but the overall effects are modest and of about the same extent as dithionite at similar levels of reduction. No extensive changes in clay structure were observed under conditions present in our model system.

Sequential cation-exchange capacity (CEC) measurements were obtained from standard clays using a mechanized, variable-rate leaching device. The device consists of a motorized screwjack and as many as 24 leaching tubes coupled to 60-ml plastic syringes. Controlled withdrawal of the syringe plungers produces a vacuum that permits samples in the leaching tubes to be extracted at a uniform rate. A single, 8-hr leaching of clays with 35 ml of salt solution was found to be comparable to multiple saturations or displacements using a centrifuge. CECs consistent with published values were obtained for reference 2:1 clay minerals using both acetate and chloride salts of Na, Ca, and Mg. Potassium-exchange capacities were also successfully measured following in situ thermal treatment of samples in the leaching tubes. Variations in measured CECs for kaolin-group minerals due to salt intercalation were minimized by using chloride rather than acetate salts and by washing with a dilute aqueous solution of the saturating cation following initial saturation. The mechanical extractor significantly reduced the effort required to perform conventional CEC determinations without sacrificing analytical precision.

Acrylamide has been polymerized between the layers of kaolinite by heat treatment. Acrylamide monomer was first intercalated by the displacement reaction between a kaolinite-N-methylformamide (NMF) intercalation compound and a 10% acrylamide aqueous solution. The resulting intercalation compound showed a basal spacing of 11.3 Å. Infrared (IR) spectroscopy and 13C nuclear magnetic resonance spectroscopy with cross polarization and magic angle spinning (13C CP/MAS-NMR) indicated the replacement of NMF by acrylamide. IR spectroscopy also showed the formation of hydrogen bonds with the hydroxyls of kaolinite. When the kaolinite-acrylamide intercalation compound was heated at 300°C for 1 hr, the basal spacing increased to 11.4 Å, and IR and 13C CP/MAS-NMR showed the disappearance of C=C bonds, indicating the polymerization of acrylamide. The heat-treated kaolinite-acrylamide intercalation compound was resistant to 30 min-washing with water, whereas the untreated kaolinite-acrylamide intercalation compound collapsed after the same treatment, an observation consistent with acrylamide polymerization between the layers of kaolinite. IR spectroscopy revealed that polyacrylamide was hydrogen bonded to kaolinite, but in a manner different from the hydrogen bonding of acrylamide.

A theoretical model describing the interaction between crystalline swelling and cation exchange selectivity is proposed for expanding 2:1 phyllosilicates. The model is based on the assumption that changes in basal spacing of a clay are phase changes, and that each phase of a clay has a different selectivity constant for a particular cation exchange reaction. Energy barriers stabilize the various phases over a limited range of interlayer ionic composition. These energy barriers cause hysteresis in crystalline swelling, which in turn causes hysteresis in cation exchange. Results are presented for an experiment involving Ba-Mg exchange on a synthetic fiuoro-hectorite. The results demonstrate key aspects of the proposed model, including a correlation between measured selectivity coefficients and basal spacings (R2 = 0.85), an abrupt change in basal spacing that corresponds with an abrupt change in selectivity and corresponding hysteresis in crystalline swelling and cation exchange selectivity. The results also demonstrate increased selectivity for the preferred cation (Ba) at high solution mole fraction of the preferred cation. This trend is opposite of that observed for heterogeneous natural smectites but consistent with predictions of the model for a homogeneous smectite.

A soil of Attica (Greece) has been studied by Mössbauer spectroscopy and magnetization measurements in order to ascertain the nature and form of iron oxides present in it. The room temperature spectra consist of a paramagnetic doublet and a small magnetic sextet. At liquid nitrogen temperature the magnetic component increases considerably at the cost of the paramagnetic component. This behavior is typical of superparamagnetism exhibited by ultrafine magnetic particles. From the values of hyperfine parameters extracted by computer fits of the spectra, the particles can be identified mainly as α-Fe2O3. The theory of superparamagnetism, in conjunction with Mössbauer and magnetization data, is discussed in detail. Application of this theory to the data for the clay fraction of the soil leads to the conclusion that the oxide particles have a size distribution with a mean particle diameter of 131 Å and a width of 14 Å.

Two clay minerals, a dioctahedral, Na-montmorillonite from Wyoming and a trioctahedral, synthetic Na-laponite, were exchanged by cupric (Cu(II)) ions and subsequently heated at 100 °C intervals up to 500 °C. The resulting materials were analyzed by chemical analysis, X-ray diffraction (XRD), cation exchange capacity (CEC) measurements, combined thermogravimetric and differential thermal analysis (TGA-DTA), infrared (IR) spectroscopy, electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS). Montmorillonite exhibits a well-known Hoffmann-Klemen effect in that, when heated, cupric (Cu) ions migrate into the lacunae of the octahedral sheet, where they compensate the negative charge deficit of the clay layer. In the case of laponite, CEC measurements and spectroscopic measurements reveal that Cu ions migrate into the octahedral sheet where they replace Li and Mg ions. After heating at 200 °C, approximately half the interlayer Cu ions are exchanged. The exchange appears to be 1 Cu for 1 Li, resulting in a slight decrease of the negative charge of the layer. After heating at 300 °C, the remaining Cu ions are exchanged by either 1 Mg or 2 Li, which does not result in any further charge reduction. At 400 °C, some of the extracted Mg remigrates into the structure and exchanges some Li (1 Mg for 2 Li). The final product at 400 or 500 °C is then a Li-laponite with Cu(II) in the octahedral sheet.

Intercalates from an ordered halloysite with urea and potassium acetate were studied using Raman microscopy. The urea intercalate showed new Raman bands at 3387, 3410, 3497 and 3598 cm−1 which were attributed to the formation of a urea-Si2O5 complex. New Raman bands were observed at 3585 and 3602 cm−1 for the potassium acetate intercalate with concomitant loss of intensity of the bands at 3635, 3655, 3675 and 3696 cm−1. These new bands were attributed to the hydrogen bonds formed between the acetate and the inner surface hydroxyl groups. Remarkable changes in intensity in the lattice region of the halloysite were observed, the foremost being the reduction of the intensity of the bands at 243, 271 and 336 cm−1. Pronounced changes in the bands at 913 and 143 cm−1 attributed to the Al-OH librations were also observed.

It is proposed that 2 distinct types of intercalation were present, as exemplified by: 1) urea intercalate, where the intercalating molecule hydrogen bonds to the Si-O of the halloysite layers and 2) potassium acetate intercalate, where the molecule is hydrogen-bonded to the inner surface hydroxyls of the halloysite layer and interacts with the tetrahedral sheet of the next adjacent halloysite layer. The Raman spectra of the intercalated halloysite strongly resembled that of an intercalated kaolinite.

Ferrihydrite prepared in different manners was kept under relative humidities ranging from 75 to 100% and at temperatures of 45° and 55°C for 180 days. Ferrihydrite transformed to hematite and goethite at relative humidities close to 100%, but at lower relative humidities the transformation was less pronounced and hematite was highly favored over goethite. Increasing temperature also favored hematite over goethite, and Al substitution completely prevented goethite formation. These results suggest that hematite can form in relatively dry, warm soils or sediments, although more slowly than in moister environments.

Bentonite, biotite, illite, kaolin, vermiculite and zeolite were treated with 0.1, 1.0 and 5.0 mol. dm−3 HCl or NaOH. Suspensions of Na homoionic forms of the initial and the treated minerals were back titrated with 0.1 mol. dm−3 NaOH. From back-titration data variable surface charge, QV, vs. pH dependencies and apparent surface dissociation constant distribution functions were estimated. Variable charge vs. pH curves were scaled against cation exchange capacity at pH 7.2 to obtain actual charge, QA, vs. pH plots. In general both treatments led to an increase of QV, while the QA value increased and decreased depending on the mineral and the treatment. Products of 5 mol dm−3 NaOH action on zeolite and of 1 and 5 mol. dm−3 NaOH on kaolin apparently developed a positive surface charge below pH ∼3.7 and below ∼4.3, respectively.

The heterogeneity of charge-generating surface groups was observed in natural minerals. During acid treatment, the number of weakly-acidic surface functional groups increased while the number of groups of stronger acidic character decreased. The opposite was found for alkaline treatment: the number of surface groups of intermediate acidity increased and that of low acidity decreased.

The nature of component layers of mixed-layer illite-smectite and their possible evolution in the course of illitization have been debated since the 1960s. The present study is a new attempt to solve these problems, using samples collected from diverse geological formations around the world. Twenty three purified illite-smectites from bentonites and hydrothermal rocks, covering the complete range of expandability, were analyzed chemically, including ${\text{NH}}_4^{+}$\$\end{document} determination, and their structural formulae were calculated. The exchangeable cations (EXCH) were plotted vs. the fixed cations (FIX) yielding the following experimental regression:$\text{EXCH}=-0.43\times \text{FIX}+0.41\left({\text{R}}^2=0.98\right)$\$\end{document}

FIX and EXCH depend on the charge of the illite (Qi) and smectite (Qs) interlayers, and the fractions of these interlayers in the bulk clay leading to: $\text{EXCH}=-Q_{\text{s}}\text{/}{Q}_{\text{i}}\times \text{FIX}+Q_{\text{s}}$\$\end{document}

Analysis of these relations and independent measurements of the total specific surface area (TSSA) indicate that the layer charges of both types do not change in the course of illitization. The smectite layer charge is equal to 0.41 and the illite layer charge is equal to 0.95 per O10(OH)2. End-member illite has a well defined composition that is close to intermediate between muscovite and phengite, with fixed cations content greater than that specified in the AIPEA classification of layer silicates:${\text{FIX}}_{0.95}\left({\text{Si}}_{3.25}{\text{Al}}_{0.75}\right)\left({\text{Al}}_{1.81}{\text{Fe}}_{0.01}{\text{Mg}}_{0.19}\right){\text{O}}_{10}{\left(\text{OH}\right)}_2$\$\end{document}

The established relationship allows the calculation of the mean number (N) of 2:1 layers in all fundamental particles and also the fraction of smectitic layers (fs) from FIX:$N=Q_{\text{i}}\text{/}(Q_{\text{i}}-\text{FIX})f_{\text{s}}=(Q_{\text{i}}-\text{FIX})\text{/}{Q}_{\text{i}}$\$\end{document}

N and fs can be used to calculate TSSA, and all three parameters can also be calculated from cation exchange capacity and from X-ray diffraction peak positions, utilizing the regressions established here.

0.5 molal iron(III) chloride solutions were hydrolysed at room temperature by base additions in the range OH/Fe mole ratio 0–2.75. After an ageing period the hydrolysed solutions were used to produce amorphous hydroxide gels from which crystalline products were grown at 65°C, at low pH or high pH. Examination of crystal composition and morphology and comparison with similarly treated nitrate solutions showed that the nucleation of hematite and goethite is inhibited in chloride containing solutions, which allow growth of small rod shaped β-FeOOH to predominate or occur exclusively in gels at pH 1–2. The addition of seed crystals of hematite and goethite allows competitive growth of all three minerals. The transformations β-FeOOH → α-Fe2O3 and β-FeOOH → α-FeOOH at pH 1–2 proceed by dissolution and reprecipitation and are promoted by adding seed crystals.

The ability of a high surface-area gibbsite to adsorb Cu2+ was studied using a Cu2+ ion-selective electrode, electron spin resonance, infrared spectroscopy, and electron microscopy. The gibbsite chemi-sorbed small amounts of monomelic Cu2+ (<0.5 mmole/100 g) which was oriented with its z-axis perpendicular to the (001) plane of the mineral. The proposed chemisorption sites are at gibbsite crystal “steps” observed by electron microscopy. Although Cu2+ adsorption on gibbsite as a function of pH was largely reversible, exposure of the chemisorbed Cu2+ to NH3 did not result in desorption from the surface despite the displacement of several OH− or H2O ligands by NH3. The results indicate that at least one Cu-O-Al bond is formed in the process of chemisorption.

At pH > 5, the gibbsite appeared to promote the hydrolysis and polymerization of Cu2+, with further adsorption at the surfaces. Infrared spectroscopy revealed no effect of the adsorption on the (001) surface hydroxyl groups, although the anisotropic diffusion of protons in the gibbsite structure was verified from deuteration studies.

The sintering of montmorillonites pillared by hydroxy-Al species was investigated by several techniques. The change of the microporosity of the pillared interlayer clay with temperature shows that sintering was mainly due to the loss of microporosity. On calcination of the parent clay at 760°C, the X-ray powder diffraction pattern did not change; the 060 line shifted only slightly from 8.988 to 9.017 Å. The infrared (IR) spectrum suggested some dehydroxylation, but the structure appears to have been preserved. On calcination of the pillared clay at >700°C, the intensity of the 001 line decreased steadily, the 060 line broadened, and the b parameter decreased slightly from 8.988 to 8.928 Å. Fe3+ ions apparently occupied only one site after calcination at 300°C and two sites after calcination at 700°C. Smaller isomer shifts and higher quadrupole splittings in the Mössbauer spectra suggest that calcination produced more covalent bonding of Fe3+ and a highly distorted structure. The IR spectrum was significantly modified by calcination of the sample, and the 935- and 1125-cm−1 bands disappeared and the 1035-cm−1 band broadened. These results suggest that at <700°C the pillars sintered and that the clay progressively decomposed at >750°C. The pillaring-induced decrease of thermal stability of the clay was likely due to the introduction of protons during the first step of the preparation. The thermal stability of these Al-pillared interlayer complexes is comparable to that reported for hydroxy-silicoaluminum montmorillonites and fluorhectorites.