Helge Stanjek

SUMMARY OF RECOMMENDATIONS OF NOMENCLATURE COMMITTEES RELEVANT TO CLAY MINERALOGY: REPORT OF THE ASSOCIATION INTERNATIONALE POUR L'ETUDE DES ARGILES (AIPEA) NOMENCLATURE COMMITTEE FOR 2006

Brindley et al. (1951) reported the earliest efforts to obtain international collaboration on nomenclature and classification of clay minerals, initiated at the International Soil Congress in Amsterdam in 1950. Since then, national clay groups were formed, and they proposed various changes in nomenclature at group meetings of the International Clay Conferences. Most of the national clay groups have representation on the Nomenclature Committee of the Association Internationale pour l’Etude des Argiles (AIPEA, International Association for the Study of Clays), which was established in 1966. The precursor committee to the AIPEA Nomenclature Committee was the Nomenclature Subcommittee of the Comite International pour l’Etude des Argiles (CIPEA, International Committee for the Study of Clays). The AIPEA Nomenclature Committee has worked closely with other international groups, including the Commission on New Minerals and Mineral Names (CNMMN) of the International Mineralogical Association (IMA), which is responsible for the formal recognition of new minerals and mineral names, and the International Union of Crystallography (IUCr), which considered extensions to the nomenclature of disordered, modulated and polytype structures (Guinier et al. , 1984) published earlier by a joint committee with the IMA (Bailey, 1977). In contrast to the other national clay groups, however, The Clay Minerals Society (CMS) Nomenclature Committee, which was established in 1963 at the same time as the CMS and predates the AIPEA Nomenclature Committee, remains in existence and occasionally produces recommendations. The precursor to this committee was the Nomenclature SubCommittee, which was organized in 1961 by the (US) National Research Council. The Chair of the AIPEA Nomenclature Committee is a standing member of the CMS Nomenclature Committee so that the committees are in close contact. The purpose of the AIPEA Nomenclature Committee has been to make general and specific recommendations concerning: (1) definitions of mineralogical and crystallographic clay-related terms; (2) classification and terminology …

QUANTITATIVE PHASE ANALYSIS OF BENTONITES BY THE RIETVELD METHOD

Thirty six bentonite samples from 16 different locations were examined in order to demonstrate the applicability of a new Rietveld description approach for quantitative phase analysis. X-ray diffraction patterns of the bulk material were obtained and analyzed by the Rietveld method. The samples contain up to ten different minerals, with dioctahedral smectite as the major component. A model for turbostratic disorder of smectites was formulated inside a structure-description file of the Rietveld program BGMN. The quality of the refinements was checked using an internal standard mineral (10.0 or 20.0 wt.% corundum) and by cross-checking results with X-ray fluorescence (XRF) data. The corundum content was reproduced with only small deviations from the nominal values. A comparison of the chemical composition obtained by XRF and the composition as re-calculated from quantitative Rietveld results shows a satisfactory agreement, although X-ray amorphous components such as volcanic glasses were not considered. As a result of this study, the Rietveld method combined with the new structure model for turbostratic disorder has proven to be a suitable method for routine quantitative analysis of bentonites with smectites as the dominant clay minerals.

Description of X-ray powder pattern of turbostratically disordered layer structures with a Rietveld compatible approach

Abstract We address the problem of the quantitative description of X-ray powder pattern of turbostratically disordered layer compounds. The Debye formula is used, which allows the aperiodic description of any arrangement of atoms. With the extension of Yang and Frindt (1996) for the ideal turbostratic case, these calculations are used to generate reference data that are subsequently treated by the Rietveld method. We are able to show that the case of uncorrelated turbostratic disorder can be modelled equally well in a periodic supercell approach with a single layer in the supercell that is suitable for the Rietveld technique. A brief introduction of this new model was given as an oral contribution at EUROCLAY 2003 (Ufer et al., 2003). The fundamental principles are described in this article because of its complexity. The applicability of this approach to real systems is demonstrated for smectite and corundum mixtures.

REPORT OF THE ASSOCIATION INTERNATIONALE POUR L’ÉTUDE DES ARGILES (AIPEA) NOMENCLATURE COMMITTEE FOR 2001: ORDER, DISORDER AND CRYSTALLINITY IN PHYLLOSILICATES AND THE USE OF THE “CRYSTALLINITY INDEX”

The purpose of this report is to describe the appropriate use of indices relating to crystallinity, such as the ‘crystallinity index’, the ‘Hinckley index’, the ‘Kubler index’, and the ‘Arkai index’. A ‘crystalline’ solid is defined as a solid consisting of atoms, ions or molecules packed together in a periodic arrangement. A ‘crystallinity index’ is purported to be a measure of crystallinity, although there is uncertainty about what this means (see below). This report discusses briefly the nature of order, disorder and crystallinity in phyllo-silicates and discusses why the use of a ‘crystallinity index’ should be avoided. If possible, it is suggested that indices be referred to using the name of the author who originally described the parameter, e.g. ‘Hinckley index’ or ‘Kubler index’, or in honor of a researcher who investigated the importance of the parameter extensively, e.g. ‘Arkai index’. In contrast to a crystalline solid, an ‘amorphous’ solid is one in which the constituent components are arranged randomly. However, many variations occur between the two extremes of crystalline vs. amorphous. For example, one type of amorphous material might consist simply of atoms showing no order and no periodicity. Alternatively, another amorphous material may consist of atoms arranged, for example, as groups of tetrahedra ( i.e. limited order) with each group displaced or rotated ( e.g. without periodicity) relative to another. Thus, this latter material is nearly entirely amorphous, but differs from the first. Likewise, disturbance of order and periodicity may occur in crystalline materials. The terms ‘order’ and ‘disorder’ refer to the collective nature or degree of such disturbances. Although seemingly simple notions, ‘crystalline’ and ‘amorphous’ are complex concepts. Crystalline substances may show a periodic internal structure based on direction. For example, two-dimensional periodicity is common in phyllosilicates where two adjacent sheets or layers must mesh. For example, in serpentine, …

Sorption of aqueous antimony and arsenic species onto akaganeite.

Two akaganeite materials were tested for the removal of antimonate, trimethyl antimonate, arsenate, arsenite, and dimethyl arsenate from water: a commercial product (GEH) and a synthesized akaganeite. The two materials show similar q(max) values, but differ in their K(L) values. This could be a result of their different crystal sizes indicated by sharper XRD reflections of the synthesized akaganeite compared with GEH. Batch experiments were carried out using all species to investigate the influence of the pH on their sorption onto the commercial material. The best results for the removal of antimonate and arsenate were achieved under acidic conditions, while the sorption of arsenite has an optimum at pH 7. The maximum loadings vary from 450 mg g(-1) (antimonate at pH 2.2.) to 2 mg g(-1) (trimethyl antimonate at pH 7). Competition reactions (up to a 10-fold excess of the competitor ion) were studied with antimonate, arsenate, and phosphate. The sorption capacity of arsenate decreases up to 12.5% by adding phosphate (ratio 1:10), but the addition of antimonate did not influence the sorption of arsenate. Conversely, the sorption of antimonate decreases due to the addition of 10-fold concentration of arsenate (31%) or phosphate (27%).

Long-term in vitro transformation of 2-line ferrihydrite to goethite/hematite at 4, 10, 15 and 25°C

Abstract 2-line ferrihydrite stored in water at ambient temperatures from 4 to 25°C and at ten different pH values between 2.5 and 12 for up to 10-12 y transformed to both goethite and hematite at all temperatures and pH values except at pH 12 where only goethite was formed. The rate and degree of transformation (20-100%) increased with increasing pH and temperature. The hematite/ (hematite+goethite) ratio varied between 0 and ~0.8, increased with increasing temperature and showed a strong maximum at pH 7-8 which increased from 0.1-0.2 at 4°C to 0.7-0.8 at 25°C. The maximum coincides with the zero point of charge of ferrihydrite where its solubility and, thus, its via-solution transformation rate to goethite are minimal. We assume, therefore, that in this pH-range the (slower) via-solution transformation to hematite can more efficiently compete with that to goethite.

Report of the Association Internationale pour l’Etude des Argiles (AIPEA) Nomenclature Committee for 2001: Order, disorder and crystallinity in phyllosilicates and the use of the ‘Crystallinity Index’

The purpose of this report is to describe the appropriate use of indices relating to crystallinity, such as the ‘crystallinity index’, the ‘Hinckley index’, the ‘Kubler index’, and the ‘Arkai index’. A ‘crystalline’ solid is defined as a solid consisting of atoms, ions, or molecules packed together in a periodic arrangement. A ‘crystallinity index’ is purported to be a measure of crystallinity, although there is uncertainty about what this means (see below). This report discusses briefly the nature of order, disorder and crystallinity in phyllosilicates and discusses why the use of a ‘crystallinity index’ should be avoided. If possible, it is suggested that indices be referred to using the name of the author who originally described the parameter, as in ‘Hinckley index’ or ‘Kubler index’, or in honour of a researcher who investigated the importance of the parameter extensively, as in ‘Arkai index’. In contrast to a crystalline solid, an ‘amorphous’ solid is one in which the constituent components are arranged randomly. However, many variations occur between the two extremes of crystalline vs. amorphous. For example, one type of amorphous material might consist simply of atoms showing no order and no periodicity. Alternatively, another amorphous material may consist of atoms arranged, for example, as groups of tetrahedra (i.e. limited order) with each group displaced or rotated (e.g. without periodicity) relative to another. Thus, this latter material is nearly entirely amorphous, but differs from the first. Likewise, disturbance of order and periodicity may occur in crystalline materials. The terms ‘order’ and ‘disorder’ refer to the collective nature or degree of such disturbances. Although seemingly simple notions, ‘crystalline’ and ‘amorphous’ are complex concepts. Crystalline substances may show a periodic internal structure based on direction. For example, two-dimensional periodicity is common in phyllosilicates where two adjacent sheets or layers must mesh. For example, …

Basics of X-ray Diffraction

X-ray diffraction (XRD) is the most comprehensive tool to identify minerals in complex mineral assemblages. The method is briefly described with special emphasis on clay and ceramics. As an example, an investigation of graphite-containing pottery sherds by XRD is presented. By comparing the measured XRD data with the patterns simulated by the Rietveld method, the graphite content of such samples could be determined.

Structural environment and oxidation state of Mn in goethite-groutite solid-solutions

Abstract Both X-ray absorption and diffraction techniques were used to study the structural environment and oxidation state of Mn in goethite-groutite solid solutions, α-MnxFe1-xOOH, with xMn ≤ 0.47. Rietveld refinement of X-ray diffraction (XRD) data was employed to investigate the statistical long-range structure. The results suggest that increasing xMn leads to a gradual elongation of Fe and Mn occupied octahedra which, in turn, causes a gradual increase of the lattice parameter a and a gradual decrease of b and c in line with Vegard’s law. X-ray absorption fine structure (XAFS) spectra at the MnKα and FeKα edges revealed, however, that the local structure around Fe remains goethite-like for xMn ≤ 0.47, while the local structure around Mn is goethite-like for xMn ≤ 0.13, but groutite-like for higher xMn. The spectral observations were confirmed by XAFS-derived metal distances showing smaller changes around Fe and larger changes around Mn as compared with those determined by XRD. Therefore, the XAFS results indicate formation of groutite-like clusters in the goethite host structure for xMn > 0.13, which remain undetected by XRD. The first prominent resonance peak in the X-ray absorption near-edge spectra (XANES) of the Mn goethites was 17.2 to 17.8 eV above the Fermi level of Mn (6539 eV), in line with that of Mn3+ reference compounds, and well separated from that of Mn2+ and Mn4+ compounds. Therefore, Mn in goethite is dominantly trivalent regardless of whether the samples were derived from Mn2+ or Mn3+ solutions. This may indicate a catalytic oxidation of Mn2+ during goethite crystal growth similar to that found at the surface of Mn oxides.

THE EFFECT OF Al ON Fe OXIDES. XIX. FORMATION OF Al-SUBSTITUTED HEMATITE FROM FERRIHYDRITE AT 25°C AND pH 4 TO 7

Iron oxides in surface environments generally form at temperatures of 25 ± 10°C, but synthesis experiments are usually done at higher temperatures to increase the rate of crystallization. To more closely simulate natural environments, the transformation of 2-line ferrihydrite to hematite and goethite at 25°C in the presence of different Al concentrations and at pH values from 4 to 7 was studied in a long-term (16–20 y) experiment. Aluminum affects the hydrolysis and charging behavior of 2-line ferrihydrite and retards crystallization. Al also promotes the formation of hematite over goethite and leads to multidomainic discoidal and framboidal crystals instead of rhombohedral crystals. The strong hematite-promoting effect of Al appears to be the result of a lower solubility of the Al-containing ferrihydrite precursor relative to pure ferrihydrite. Hematite incorporates Al into its structure, as is shown by a decrease in the a and c-cell lengths and a decrease in magnetic hyperfine fields (Mössbauer spectroscopy). With hematite formed at low-temperature, these decreases were, however, smaller for the cell length and greater for the magnetic field than for hematite produced at higher temperatures. Both phenomena are removed by heating the hematite at 200°C. They are attributed to structural OH and/or structural defects. The relative content of Al in the structure is lower for hematite formed at 25°C than for hematites synthesized at higher temperatures (80 and 500°C). The maximum possible substitution of one sixth of the Fe positions was not achieved, similar to soil hematites. These results show that properties of widely distributed soil Al-containing hematites can reflect formation environment.