Smectite growth is of importance across various fields due to its abundance on the surface of both Earth and Mars. However, the impact of the crystallinity of initial materials on smectite growth processes remains poorly understood. In this study, the kinetic processes of smectite growth were examined via experimental synthesis of trioctahedral Mg-Ni saponites. Mg-Ni saponites were synthesized using mixed precursors, specifically end-member Mg-saponite and Ni-saponite, which exhibit different crystallinities. The crystal chemistry and morphology of samples were analyzed using X-ray diffraction, Fourier-transform infrared spectroscopy, and high-angle annular dark-field scanning transmission electron microscopy. The experimental results converge towards these main conclusions: (i) the formation of Mg-Ni saponite solid solutions are promoted when the precursors are small particles, whereas large-particle precursors limit their own dissolution and do not yield Mg-Ni saponite solid solutions under the experimental conditions; (ii) because Ni exhibits a greater stability within the saponite structure compared to Mg, the Mg-Ni-saponite solid solutions formed more easily from the mixture of Ni-saponite germs and well-crystallized Mg-saponite precursors than from the mixture of Mg-saponite germs and well-crystallized Ni-saponite precursors; (iii) the dissolution extent (DE) of precursor mixtures increases with longer synthesis time, higher synthesis temperature, and larger gap between synthesis temperature of precursors and of samples, and stabilizes once it reaches a certain value. Thus DE can be used to estimate the kinetics of Mg-Ni saponite crystallization from precursor mixtures. These results obtained from the experimental Mg-Ni saponite system are useful for predicting the evolution processes of smectite in natural systems.

This study examines the origin and distribution of clay minerals of the pedological horizons of Kori Ouallam watershed (south-western Niger). It is based on field sampling campaigns and a series of laboratory analyses. A total of 49 samples were analysed, 28 from surface horizons (0–10 cm depth) and 21 from pedological profiles (0–1 m depth). The samples were analysed by X-ray diffraction on bulk and clay (<2 μm) fractions, X-ray fluorescence spectrometry, laser granulometry, organic matter and calcium carbonate content, macroscopic observations (binocular loupe) and scanning electron microscopy equipped with an energy-dispersive spectrometry system. The pedological horizons are characterized by low organic matter contents (<1%) and no calcium carbonate. The particle-size distribution shows net textural differentiation, with a predominance of sandy loam to sandy clay loam textures in the upper horizons and clay loam to clay in the deep horizons. The main major oxides were SiO2 (46.3–89.0%), Al2O3 (5.0–24.2%) and Fe2O3 (1.0–27.9%). Kaolinite (64–98%) is the predominant clay mineral at all horizons, associated with low to moderate proportions of illite (1–34%) and traces of chlorite. Kaolinite is essentially inherited from the parent rock, whereas illite results from chemical alteration by bisialitization of the primary minerals initially rich in potassium feldspar contained in the parent rock. However, soil texture and organic matter vary independently with clay mineralogy. An extended study of all of the pedological facies that make up south-western Niger, combined with supplementary analyses, would further improve our understanding of clay mineralogy in the Sahelian zone.

Illite is a common clay mineral that is found in a wide range of geological settings. The good thermal stability and non-swelling properties of illite make it valuable in ceramic materials, paints and coatings, drilling fluids, agriculture and geological studies. To gain a deeper understanding of the physical and chemical properties of illite, in the present paper the atomic and electronic structures of a typical trans-vacant 1M Al-rich illite were constructed and calculated using density functional theory. The calculated indirect band gap of Al-rich illite was 4.99 eV. The electronic analysis revealed that the interactions in the tetrahedral sheet were more stable than those in the octahedral sheet. The substitution of Al atoms noticeably reduced the stability of the tetrahedral sheet in Al-rich illite. Other properties of Al-rich illite, including the density of states, electron population/charge, electronic charge density and bonding interaction, are also discussed and analysed in detail.

A series of natural clays, including 1:1 layer silicates (serpentines, kaolin minerals), smectites, vermiculite, micas, talc, pyrophyllite, sepiolite, and palygorskite, were studied by 19F magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The 19F chemical shift in these layer silicates is characteristic of the structure, in particular, to the local octahedral cation occupancy. Fluoride ions bonded to three Mg octahedral cations have a chemical shift of about −177 ppm and those bonded to two Al cations and a vacancy have a chemical shift of about −134 parts per million (ppm). The shift at −182.8 ppm in hectorite is apparently associated with fluoride bonded to two Al cations and a Li cation. Surprisingly, the difference in chemical shift of the interlayer and inner fluoride in 1:1 layer silicates is insufficient to distinguish these sites. Based on trends in chemical shift, it appears that fluoride substitution for inner hydroxyls in clays with octahedral substitution is not random. Fluoride is apparently preferentially associated with Mg rather than Al in the octahedral sheet as no resonance due to a fluoride bonded to two Al cations and a vacancy is observed in clays such as SAz-1.

Clay mineralogical studies by X-ray diffraction performed on extracted <2-µm fractions do not always represent all clay mineral constituents present in the soil. In this work, transmission X-ray diffraction (TXRD) was applied to undisturbed microsamples of optically homogeneous mineral soil fabrics and features. These microsamples were isolated by microdrilling their periphery in soil thin sections, then removing them, and transferring them to glass capillaries for TXRD analysis. The usefulness of this technique for supplying in situ mineralogical information on identification, structure, and natural orientation of soil constituents was tested on mineral microfabrics and features of primary and secondary phyllosilicates. The study demonstrated that TXRD allowed detailed, representative interpretations of undisturbed mineral features and fabrics. In particular, this technique allowed us (1) to compare mineralogical compositions at selected microlocalities, (2) to study natural preferred orientations, and (3) to detect small amounts of minor mineral interstratification phases. In addition, complementary information on crystallography and crystal chemistry may be obtained by performing analytical transmission electron microscopy on the same microsample.

Diffusion of alkali and low-atomic-number elements during the microbeam analysis of some silicates by analytical electron microscopy (AEM) has been known for some time. Our repeated analyses at 300 kV of kaolinite, halloysite, smectite, biotite, muscovite and pyrophyllite, however, showed differential loss (relative to Si) of not only alkali elements (such as K, Na, Mg) and low-atomic-number elements (such as Al) but also higher-atomic-number elements (such as Fe, Ti). For AEM of these phyllosilicates, a Philips EM430/EDAX facility with a tungsten filament was used to provide a current of 0.3 nA in a stationary beam of nominal diameter 90 nm. The loss of Al in kaolin minerals during analysis is particularly severe. Kaolin crystals can be damaged by the electron irradiation over several seconds, making it the most sensitive clay to the electron beam; in general, relative phyllosilicate stabilities are kaolin < smectite < pyrophyllite < mica. A clear dependence of element loss on crystallographic orientation has been observed for layer silicates in our study; a greater element loss occurred when the plane of the specimen foil was perpendicular to the basal planes of the phyllosilicate crystals than when the foil was parallel to the basal planes. Lower beam current, larger beam diameter and thicker specimens all reduce the loss of elements. The initial stage of irradiation produces highest rates of element loss and the rate of loss can be fitted by an exponential decay law. The analyses at low temperature of phyllosilicates showed that element loss remains serious in our analytical conditions. Since the element loss appears to be instrument- and method-dependent, one should use closely related, well-characterized phyllosilicates as compositional standards to calibrate any AEM instrument that is to be used to analyze unknown phyllosilicates, and the standards and unknowns should be analyzed under identical conditions.

This paper thoroughly describes the decomposition procedure, using the example of DECOMPXR (Lanson 1990). The steps of the decomposition procedure are: 1) preliminary data processing; 2) decomposition; 3) validation of results; and 4) use of the results. The use of decomposition is restricted to the separation of contributions from various phases. The effect of preliminary data processing steps (data smoothing, background stripping) on profile shape is shown to be limited and their implementation is detailed. Potential experimental limitations such as peak symmetry, experimental reproducibility or discrimination are equally minor. A logical decomposition process starts from the definition of the angular range to be fitted, proceeds with the determination of the number of elementary peaks to be fitted and ends with the check for results consistency.

Numerical data processing is a powerful tool for the accurate identification of monophases, because of the additional parameters available to constrain XRD profile simulation. Ultimately, however, the match over the whole angular range of both the experimental and the simulated patterns remains the only valid way to characterize the phases present in the sample. Additionally, the decomposition procedure permits both the identification of complex clay mineral assemblages and the characterization of their evolution. This step constrains, and may help to determine, the reaction mechanisms of a transformation; and, as a consequence, to characterize and to model the kinetics of this transformation.

Extensive hydrothermal alteration is observed around volcanogenic massive sulfide deposits. These deposits are related to Late Cretaceous volcanism in various parts of the Eastern Pontide province. Mineral assemblages resulting from alteration consist of mostly clay minerals and silica polymorphs, some sulfate minerals, and scarce zeolite minerals. The clay minerals are kaolinite, illite, and smectite. These minerals were examined using X-ray diffraction (XRD), scanning electron microscopy (SEM)-energy dispersive spectrometry (EDS), X-ray fluorescence spectroscopy (XRF), and differential thermal analysis (DTA)-thermal gravimetry (TG) techniques. The illite and the toseki deposits are a result of hydrothermal alteration of dacitic-andesitic volcanites. Two groups of bentonite deposits occur; the first mainly formed by hydrothermal solution whereas the second group resulted from halmyrolysis.

The smectite in these alteration zones is generally montmorillonitic in composition and the interlayer cation is mostly Ca and lesser amounts of Na. The SiO2 and Fe2O3 contents of the hydrothermal bentonites are higher than those of the halmyrolysis smectites; however, the MgO content of both groups is similar. The Na2O and K2O contents of both groups are generally <0.5%. The hydrothermal bentonites are not plastic and have open honeycomb microtextures, although the halmyrolitic smectites are plastic with ultrafine and rod-shaped textures. Illite, which contains some smectite layers, is a 1M polymorph, and has an asymmetry to the low-angle side of the XRD peaks. The impure illite deposits contain various combinations of smectite, kaolinite and gypsum, galena, sphalerite, pyrite, goetite, and quartz. The illite has >35 wt. % Al2O3. The toseki raw material, which may be possibly useful as a porcelain raw material, is composed mainly of illite, kaolinite and quartz, or illite and quartz. The crystallinity of the kaolinite is poor.

An internal standard X-ray diffraction (XRD) analysis technique permits reproducible and accurate calculation of the mineral contents of rocks, including the major clay mineral families: Fe-rich chlorites + berthierine, Mg-rich chlorites, Fe-rich dioctahedral 2:1 clays and micas, Al-rich dioctahedral 2:1 clays and micas, and kaolinites. A single XRD pattern from an air-dried random specimen is used. Clays are quantified from their 060 reflections which are well resolved and insensitive to structural defects. Zincite is used as the internal standard instead of corundum, because its reflections are more conveniently located and stronger, allowing for a smaller amount of spike (10%). The grinding technique used produces powders free of grains coarser than 20 µm and suitable for obtaining random and rigid specimens.

Errors in accuracy are low, <2 wt. % deviation from actual values for individual minerals, as tested on artificial shale mixtures. No normalization is applied and thus, for natural rocks, the analysis is tested by the departure of the sum of the measured components from 100%. Our approach compares favorably with other quantitative analysis techniques, including a Rietveld-based technique.

This paper deals with the use of Stern theory as applied to a clay-water electrolyte system, which is more realistic to understand the force system at micro level than the Gouy-Chapman theory. The influence of the Stern layer on potential-distance relationship has been presented quantitatively for certain specified clay-water systems and the results are compared with the Gouy-Chapman model. A detailed parametric study concerning the number of adsorption spots on the clay platelet, the thickness of the Stern layer, specific adsorption potential and the value of dielectric constant of the pore fluid in the Stern layer, was carried out. This study investigates that the potential obtained at any distance using the Stern theory is higher than that obtained by the Gouy-Chapman theory. The hydrated size of the ion is found to have a significant influence on the potential- distance relationship for a given clay, pore fluid characteristics and valence of the exchangeable ion.

Consideration of XRD, TEM, AEM, and analytical data reported in the literature indicates that dioctahedral aluminous smectite and illite form two separate solid solutions that differ chemically from one another primarily by the extent of Al substitution for Si, the amount of interlayer K, and the presence of interlayer H2O. The data indicate that limited dioctahedral-trioctahedral and dioctahedral-vacancy compositional variations occur in both minerals. Excluding interlayer H2O and based on a half unit cell [i.e., O10(OH)2], natural dioctahedral smectite and illite solid solutions fall within the compositional limits represented by A0.3${\rm{R}}_{1.9}^{3 + }$Si4O10(OH)2-AR2+ R3+ Si4O10(OH)2-A0.25${\rm{R}}_{0.3}^{2 + }{\rm{R}}_{1.8}^{3 + }$Al0.25Si3.75O10(OH)2 for smectites and A0.8${\rm{R}}_{1.9}^{3 + }$Al0.5Si3.5O10(OH)2-A0.55${\rm{R}}_{0.45}^{2 + }{\rm{R}}_{1.55}^{3 + }$Al0.1Si3.9O10(OH)2-A0.9${\rm{R}}_{0.3}^{2 + }{\rm{R}}_{1.8}^{3 + }$Al0.9Si3.1O10(OH)2 for illites, where A represents either monovalent cations or divalent cations expressed as their monovalent equivalent (e.g., Ca2+/2); R2+ stands for the divalent cations Mg2+ and Fe2+ and R3+ refers to the trivalent cations Al3+ and Fe3+. Taking account of these compositional limits, smectite and illite solid solutions can be described in terms of nine and six thermodynamic components, respectively, all of which are consistent with both the law of definite proportions and the concept of a unit cell. Thermodynamic components that can be used to describe natural smectite solid solutions in terms of a half unit cell [i.e., O10(OH)2] can be expressed as NaAl3Si3O10(OH)2, NaAl3Si3O10(OH)2 ·4.5H2O, Al2Si4O10(OH)2, Fe2Si4O10(OH)2, Mg3Si4O10(OH)2, Fe3Si4O10(OH)2, K3AlSi4O10(OH)2, KAl3Si3O10(OH)2, and Ca0.5Al3Si3O10(OH)2. Of these, NaAl3Si3O10(OH)2 ·4.5H2O provides explicitly for the presence of interlayer H2O in the mineral. Thermodynamic components representing illite solid solutions in natural systems can be written for a half unit cell as KAl3Si3O10(OH)2, KMg3AlSi3O10(OH)2, KFe3AlSi3O10(OH)2, Al2Si4O10(OH)2, KFe2AlSi3O10(OH)2, and K3AlSi4O10(OH)2. The calculations and observations summarized below indicate that neither smectite nor illite occur in nature as stoichiometric phases and that the two minerals do not form a mutual solid solution corresponding to mixed-layered illite/smectite.

An improved regression method for the evaluation of standard free energies of formation (ΔG°f) of clay minerals is here proposed in an attempt to remove some of the limitations of the earlier method (Chen, 1975). Particularly, this method suggests a procedure for the assignment of rankings for Σ ΔG°f, i values. Moreover, an iterative least-squares fitting technique is applied to solve the exponential equation to obtain the estimated ΔG°f. The estimated ΔG°f data for the various standard clay minerals are derived and compared with data available in the literature; in general, there is good agreement between the values. It is also shown how the regression method can be extended to clay minerals of variable composition. The ΔG°f's for several such minerals have been evaluated; a large number of combination equations required for such computations have been listed, so that for other similar minerals the process of evaluation of ΔG°f is greatly simplified.

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

Three ball clays (SP from England, TSMA from France and UK from the Ukraine) were characterized for their dry and wet colloidal properties. On the basis of X-ray diffraction and chemical analyses the clays were classified as kaolinite-rich clay, smectitic kaolinite-rich clay and illitic kaolinite-rich clay. The ζ (zeta) potential at the clay-water interface as a function of pH, in three different electrolytes, was investigated using an electroacoustic technique. Starting from measurements of dynamic mobility, the calculated ζ potential was found to be almost constant as a function of pH for the TSMA and UK clays, while it increased from −20 to −60 for the SP clay, when potassium nitrate was used as an electrolyte. The behavior of the three clays in calcium and magnesium nitrate was slightly different: SP showed a smaller increase in ζ potential, while a small deviation from the constant behavior of the UK clay was found. The results are explained in terms of the surrounding-ion atmosphere in light of the chemical-physical properties measured. Our results may well be of use to those involved in ceramic processing.

High-resolution solid-state, fluorine-19, magic-angle spinning-nuclear magnetic resonance spectroscopy (MAS-NMR) was used to study natural and synthetic fluorinated 2:1 layer silicates of known composition. This technique enabled us to determine directly the coordination of structural fluorine and it was found to be sensitive to both the chemical nature of the octahedral elements (Al, Mg, Li) and the type of octahedral sheet (di- or trioctahedral). The observed chemical shifts at −132, −152, −176 and −182 ppm (relative to CFC13) were assigned to different environments of fluorine. The results were then used to characterize synthetic 2:1 layer silicates with unknown octahedral composition.

The smectite-to-illite diagenetic transformation has been documented in 5 different sedimentary basins using X-ray diffraction (XRD). Intermediate reaction products coexisting because of the effect of kinetics on this reaction have been characterized using decomposition of XRD patterns and comparison with calculated patterns. The nature and relative abundances of the various subpopulations of particles are shown to vary as a function of the geothermal gradient and of the age of the sediment. In all sedimentary basins that experienced a low steady geothermal gradient the physico-chemical characteristics (coherent scattering domain size [CSDS], junction probabilities) of intermediate mixed-layered illite-smectites (I-S) are similar. However, both the relative abundance and the crystallinity of the end-member illite increase as a function of the age of the sediment.

In basins that have experienced a higher geothermal gradient, the CSDS of the I-S subpopulation is higher for a given illite content, indicating a slightly different reaction pathway. This difference in the characteristics (peak position and width) of elementary peaks may be used to infer the presence of such a high geothermal gradient when no other data are conclusive. In this case the growth of the illite end-member is favored over the growth of intermediate I-S phases even in young basins. Illitic phases formed from the alteration of kaolin minerals exhibit characteristics similar to the reaction products of the smectite-to-illite diagenetic transformation in the case of a high geothermal gradient. In contrast with what is observed in shale diagenesis, the characteristics of the illitic subpopulations describe a continuum with absolutely no gap in between subpopulations. In sandstone reservoirs, the various subpopulations crystallize simultaneously from a kaolin precursor. As a consequence, no kinship is expected between the various subpopulations.

Knowledge of clay mineralogy is essential for understanding the source areas and weathering environments of fluvial sediments, particularly in large reservoirs facing serious problems with sediment deposition, such as the Three Gorges Reservoir (TGR) in east-central China. The purpose of the present study was to identify the sediment provenances and weathering regimes contributing to the sediment load in the TGR by determining the clay-mineral and geochemical compositions of surface sediments during various seasons. X-ray diffractometry and scanning electron microscopy (SEM) were used to identify the clay minerals. The results showed that illite was the dominant mineral, followed in order by kaolinite, chlorite, and montmorillonite. From a mineralogical perspective, distal sources were the main contributors to the TGR sediments, and regional sources (surrounding tributaries) also contributed much during the three seasons, while proximal sources (hillslope soils) supplied sediment in the flood season but not in the other two seasons. The geochemical and hydrological data generally supported the mineralogical results. In the flood season, the chemical indices of the TGR sediments were >0.4, showing that the sediments contained Al-rich illite minerals and experienced intense hydrolysis. In the other two seasons the TGR sediments were enriched in Fe- and Mg-rich illite minerals, resulting from strong physical weathering. Furthermore, precipitation, rather than air temperature or latitude, was the factor that controlled weathering intensity. These findings provide deep insights into the sediment cycle and chemical weathering in this large reservoir basin.

Ultrathin sections of reference 2:1 layer silicates treated with octadecylammonium cations were examined using high-resolution transmission electron microscopy (HRTEM) to establish the layer structure. Hitherto, few HRTEM ultrathin-section data existed on the expansion behavior of smectite-group minerals with different interlayer-charge values. Without such information, the expansion behavior of both low-charge and high-charge smectite minerals cannot be characterized and the structures observed in HRTEM images of clay-mineral mixtures cannot be interpreted reliably. Reference smectite-group minerals (Upton, Wyoming low-charge montmorillonite; Otay, California high-charge montmorillonite; a synthetic fluorohectorite; and a Jeanne d’Arc Basin offshore Newfoundland clay sample) with a range of layer charge values were examined. To prevent possible intrusion of epoxy resin into interlayers during embedding, the clay samples were first embedded in epoxy, sectioned with an ultra microtome, and then treated with octadecylammonium cations before examination using HRTEM. Lattice-fringe images showed that lower-charge (<0.38 eq/O10(OH)2) 2:1 layers had 13–14 Å spacings, whereas higher-charge (>0.38 eq/O10(OH)2) 2:1 layers had 21 and 45 Å spacings. These differently expanded silicate layers can occur within the same crystal and an alternation of these layer types can generate rectorite-like structures. For comparison, clay samples were also treated with octadecylammonium before epoxy embedding and sectioning and then examined with HRTEM. These samples mostly had highly expanded interlayers due to epoxy intrusion in the interlayer space. The reference clay minerals embedded in epoxy resin, sectioned, and treated with octadecylammonium cations were used to characterize smectite-group minerals in a natural clay sample from the Jeanne d’Arc Basin, Eastern Canada. Smectite-group minerals in this sample revealed similar structures in lattice-fringe images to those observed in the pure reference clay samples. Rectorite-like structures observed in lattice-fringe images were in fact smectite crystals with short, alternating sequences of low-charge and high-charge smectite layers rather than illite-smectite (I-S) phases with expanded smectite layers and non-expanded 10 Å illite layers.

The mineralogical properties of goethite and clay minerals from the Shewushan supergene gold deposit have been studied using X-ray diffraction (XRD) and transmission electron microscopy (TEM). These results show that in the weathering zone of the Shewushan supergene gold deposit the mineral assemblage is mainly composed of quartz, kaolinite, halloysite, minor illite and goethite. The coexistence of these minerals is apparently indicative of weak laterization. The Al content in goethite from XRD data is ∼10.0%, suggesting formation by weak desilicification. Observation by TEM shows that the flakes of clay minerals with larger particle size usually have extremely rounded outlines, indicating intensive dissolution of clay minerals. Halloysite is derived from the decomposition of kaolinite and the micrographs of curling, tubular, and club-shaped halloysite strongly suggest significant hydration and thus a water-saturated environment. Both the XRD data of goethite and the micrographs of the clay minerals show that the environment in Shewushan is characteristic of high [H2O] activity and high [SiO2] activity. The high dynamic hydraulic conditions may facilitate the downward migration of the primary gold particles during their mechanical concentration, resulting in the accumulation of gold in the lower portion near the water table.

Details of the quantitative techniques successfully applied to artificial rock mixtures distributed for the third Clay Minerals Society Reynolds Cup (RC) contest are presented. Participants each received three samples, two containing 17 minerals each and a third containing ten minerals. The true composition of the samples was unknown to all participants during the contest period. The results submitted were ranked by summing the deviations from the actual compositions (bias). The top three finishers used mainly X-ray diffraction (XRD) for identification and quantification. The winner obtained an average bias of 11.3% per sample by using an internal standard and modified single-line reference intensity ratio (RIR) method based on pure mineral standards. Full-pattern fitting by genetic algorithm was used to measure the integrated intensity of the diagnostic single-line reflections chosen for quantification. Elemental-composition optimization was used separately to constrain phase concentrations that were uncertain because the reference mineral standards were lacking or not ideal. Cation exchange capacity, oriented-sample XRD analysis, and thermogravimetric analysis were also used as supplementary techniques. The second-place finisher obtained an average bias of 13.9%, also by using an RIR method, but without an added internal standard and with intensity measured by whole-pattern fitting. The third-place finisher, who obtained an average bias of 15.3%, used the Rietveld method for quantification and identification of minor phases (using difference plots). This participant also used scanning electron microscopy (with X-ray microanalysis) to identify minor components and verify the composition of structures used in Rietveld analysis. As in the previous contests, successful quantification appears to be more dependent on analyst experience than on the analytical technique or software used.