The emergence of Sardis as an urban centre in the early Iron Age coincided with local production of fine painted pottery in a distinctive regional idiom. Examples of Lydian-style pottery found across western Anatolia from the eighth century BC attest the city’s growing cultural and economic contacts as well as consistent materials and craft methods. Archaeo- metric study using neutron activation analysis (NAA) at the University of Missouri Research Reactor (MURR) examined representative specimens of Lydian-style ceramics from Sardis and compared their composition with later examples of red-gloss and red-slipped pottery, fine grey wares and transport jars commonly found at the site. The results confirm the sustained activity of local workshops from the early Iron Age into later historical periods, as Lydia became part of the Seleucid and Roman empires and Sardis a centre of regional innovation.

Recently, significant advances have been made in the theory and application of acoustic and electroacoustic spectroscopies for measuring the particle-size distribution (PSD) and zeta potential (ζ potential) of colloidal suspensions, respectively. These techniques extend or replace other techniques, such as light-scattering methods, particularly in concentrated suspensions. In this review, we summarize acoustic and electroacoustic theory and published results on clay mineral suspensions, detail theoretical constraints, and indicate potential applications for the study of environmentally significant clay mineral suspensions. Using commercially available instrumentation and suspension concentrations up to 45 vol.%, acoustic spectroscopy can characterize particle sizes from 10 nm to 10 µm, or greater. Electroacoustic spectroscopy can determine the ζ potential of a suspension with a precision and accuracy in the mV range. Despite the clear potential for their use in environmental settings, to date, acoustic methods have been used mainly on clay mineral colloids with industrial application, typically combined with similar measurements such as isoelectric point (IEP) determined from shear yield stress or ζ potential from electrophoretic mobility measurements. Potential applications in environmentally relevant suspension concentrations are significant, as PSD and ζ potential are important factors influencing the transport of mineral colloids and associated contaminants through porous media. Applications include determining the effects of suspension concentration, surfactants, electrolyte strength, pH and solution composition on soil clay properties and colloidal interactions, and determining changes in PSD, aggregation and ζ potential due to adsorption or variations in the clay mineralogy.

Literature and history as objects of study and fields of inquiry have shaped each other in profound if asymmetrical ways. This introduction provides a brief account of how these disciplines intersect in the GAPE and the contemporary era, emphasizing concerns with expertise and amateurism that also emerge in many of the articles in this special issue. Those concerns, in turn, relate to what the articles show are literature’s pedagical functions in the GAPE and the present moment and within and beyond the classroom. As it argues, literature’s pedagogical dimensions challenge distinctions between teaching, research, and activism in the context of current debates about if and how historical and literary study should be presentist and politically committed.

The surface acidic properties of pillared clays (PILCs) with Al or Zr oxide pillars (prepared from a natural Portuguese smectite and a synthetic Laponite), and of a protonic NaHY zeolite, were studied by two methods: pyridine adsorption followed by infrared (IR) spectroscopy, and the catalytic transformation of 1-butene. The results of the pyridine adsorption revealed that all the pillared clays studied have mainly Lewis-type acidity, the exception being the clay pillared with Zr oxide, obtained from natural smectite, which also presents a significant number of Brönsted acid sites. The results of 1-butene transformation showed that the pillared clays exhibit catalytic properties similar to those of the protonic Y zeolite. The acid character of the solids was confirmed by the values of the cis/trans 2-butene isomers ratio. At short reaction times, product distribution showed that the main reaction is oligomerization, followed by cracking. After 15 min the products are mainly the linear isomers, cis and trans-2-butene, showing that the majority of the catalytic active sites, are already poisoned after 15 min of reaction. The particular behaviour of Laponite intercalated with Al oxide pillars is discussed. The IR spectra of the pyridine adsorbed on the fresh samples and after the catalytic assays, revealed that Lewis acid sites behave as active sites for 1-butene catalytic transformation. The consistency between the results of the two complementary techniques used for the characterization of the acidity of the solids was proved.

Electron energy-loss spectroscopy (EELS), energy-filtered transmission electron microscopy (EFTEM), and high-resolution transmission electron microscopy (HRTEM) have been applied in mineralogy and materials research to determine the oxidation states of various metals at high spatial resolution. Such information is critical in understanding the kinetics and mechanisms of mineral–microbe interactions. To date, the aforementioned techniques have not been applied widely in the study of such interactions. In the present study, the three techniques above were employed to investigate mineral transformations associated with microbial Fe(III) reduction in magnetite. Shewanella putrefaciens strain CN32, a dissimilatory metal-reducing bacterium, was incubated with magnetite as the sole electron acceptor and lactate as the electron donor for 14 days under anoxic conditions in bicarbonate buffer. The extent of bioreduction was determined by wet chemistry and mineral solids were investigated by HRTEM, EFTEM, and EELS. Magnetite was partially reduced and biogenic siderite formed. The elemental maps of Fe, O, and C and red-green-blue (RGB) composite map for residual magnetite and newly formed siderite were contrasted by the EFTEM technique. The HRTEM revealed nm-sized magnetite crystals coating bacterial cells. The Fe oxidation state in residual magnetite and biogenic siderite was determined using the EELS technique (the integral ratio of L3 to L2). The integral ratio of L3 to L2 for magnetite (6.29) and siderite (2.71) corresponded to 71% of Fe(III) in magnetite, and 24% of Fe(III) in siderite, respectively. A chemical shift (~1.9 eV) in the Fe-L3 edge of magnetite and siderite indicated a difference in the oxidation state of Fe between these two minerals. Furthermore, the EELS images of magnetite (709 eV) and siderite (707 eV) were extracted from the electron energy-loss spectra collected, ranging from 675 to 755 eV, displaying different oxidation states of Fe in the magnetite and siderite phases. The results demonstrate that EELS is a powerful technique for studying the Fe oxidation-state change as a result of microbial interaction with Fe-containing minerals.

The purification of clay minerals prior to their use as catalysts can escalate processing costs so methods are needed whereby less purification is necessary. One such potential method is acid treatment of the unpurified clay minerals. The main objectives of the present study were to develop the optimal acid-treatment conditions and to determine how the acidic properties of the modified clay samples influenced their catalytic capability toward the dehydration of ethanol and methanol. Clay mineral samples – allophane, palygorskite, and sepiolite, without purification – were acid treated (0.8 M HNO3; 95°C; 2, 8, or 24 h) and after calcination (500°C; 6 h) tested as catalysts for the conversion of methanol to dimethyl ether and of ethanol to diethyl ether and ethene. The changes in chemical and structural compositions as well as surface acidity of the mineral samples were analyzed and correlated with their catalytic performance. Among the samples studied, allophane was the most catalytically active in the dehydration of methanol to dimethyl ether. Acid treatment of this mineral sample decreased methanol conversion slightly. An opposite effect was found for ethanol dehydration to diethyl ether, where acid treatment increased catalytic activity of allophane. The differences in catalytic performance of the mineral samples were discussed with respect to the nature and concentration of acid sites.

The adsorption of the herbicides quinmerac 7-chloro-3-methylquinoline-8-carboxylic acid (QMe) and quinclorac 3,7-dichloroquinoline-8-carboxylic acid (QCl) on homoionic Fe3+-, Al3+-, Cu2+-, Ca2+-, K+- and Na+-exchanged montmorillonite was studied in aqueous solution. Adsorption data were fitted to the logarithmic form of the Freundlich equation. Ca- and Na-exchanged montmorillonites were ineffective in the adsorption of QMe. On the other hand, the QMe adsorption on Fe-exchanged montmorillonite was rapid and the equilibrium was attained after 15 min. An H-type isotherm was observed for the QMe adsorption on Fe-clay, indicating a high affinity of the solute for the sorption sites and almost complete adsorption from dilute solution. On the other hand, the adsorption isotherm of QMe on Al- and K-clay was of the S-type. This shape suggests that the solvent molecules may compete for the sorption sites. A Fourier transform infrared (FTIR) study suggested that the adsorption mechanism of QMe on Fe-, Al- and K-clay involves the protonation of QMe molecule due to the acidic water surrounding the saturating cations. The greater acidity of Fe-clay compared with Al- and K-clay explains both the lower QMe adsorption observed on Al and K systems and the lack of adsorption on Na and Ca systems. In contrast, the formation of a Cu complex permitted QMe to be adsorbed to a large extent to Cu-clay as shown by FTIR analysis. The QCl was adsorbed only by Fe-clay and the adsorption isotherm of QCl on Fe clay was of the S-type. This finding is consistent with the lower basic character of the QCl molecule nitrogen. In fact, the replacement of the electron-releasing methyl group in QMe with an electron-withdrawing Cl atom to form QCl makes the nitrogen lone-pair electrons of the quinoline ring unavailable for either protonation or complexation.

Fe is a common substituent in palygorskites (Plg), but its effect on the microscopic properties is unclear. In the current study, molecular dynamics (MD) simulations were carried out to investigate the effect of Fe on the properties of the nano-pores in Plg. The structures and dynamics of water and Na+ ions in the pores were computed by analyzing the MD trajectories. The results revealed that for both Fe-containing and ordinary Plg, zeolitic water molecules can diffuse into the pores with very low mobility whereas Mg-coordinated water fails to escape. Na+ ions show no obvious diffusivity because they are fixed above the Si–Osix-membered rings. Detailed comparison indicates that Fe-substitution has no significant influence on the pore properties of Plg.

Montmorillonites, with the general composition where x = ξ = 0.2–0.6, x = y+z, and y≪z, vary widely in composition and structure. The commonly used classification into five montmorillonite and two beidellite groups for the solid-solution sequence does not allow an unambiguous classification with respect to structural features and the resulting properties.

The smectite structure reveals five features that allow an unambiguous description of a sample: (1) identification as either a dioctahedral or a trioctahedral smectite; (2) layer charge; (3) charge distribution between tetrahedral and octahedral sheets; (4) cation distribution within the octahedral sheet; and (5) Fe content. In addition, the nature of interlayer cations should be given as they influence certain properties of montmorillonites. Analytical methods are now available to measure and determine these structural features. Therefore, a precise classification for montmorillonites requires determination of layer charge and exchangeable cations, analysis of chemical composition, and thermal analysis (to determine the octahedral structure), in addition to X-ray diffraction analysis.

A comprehensive classification of montmorillonites based on these parameters is proposed. Ninety-six structural variations (expressed by systematic names) theoretically exist within the montmorillonite-beidellite series. Descriptive names can be used to elucidate the macroscopic properties of the montmorillonite samples in question.

In water-rich smectite gels, bound or less mobile H2O layers exist near negatively-charged clay platelets. These bound H2O layers are obstacles to the diffusion of unbound H2O molecules in the porespace, and therefore reduce the H2O self-diffusion coefficient, D, in the gel system as a whole. In this study, the self-diffusion coefficients of H2O molecules in water-rich gels of Na-rich smectites (montmorillonite, stevensite and hectorite) were measured by pulsed-gradient spin-echo proton nuclear magnetic resonance (NMR) to evaluate the effects of obstruction on D. The NMR results were interpreted using random-walk computer simulations which show that unbound H2O diffuses in the gels while avoiding randomly-placed obstacles (clay platelets sandwiched in immobilized bound H2O layers). A ratio (volume of the clay platelets and immobilized H2O layers)/(volume of clay platelets) was estimated for each water-rich gel. The results showed that the ratio was 8.92, 16.9, 3.32, 3.73 and 3.92 for Wyoming montmorillonite (⩽ 5.74 wt.% clay), Tsukinuno montmorillonite (⩽ 3.73 wt.% clay), synthetic stevensite (⩽ 8.97 wt.% clay), and two synthetic hectorite samples (⩽ 11.0 wt.% clay), respectively. The ratios suggest that the thickness of the immobilized H2O layers in the gels is 4.0, 8.0, 1.2, 1.4 and 1.5 nm, respectively, assuming that each clay particle in the gels consists of a single 1 nm-thick platelet. The present study confirmed that the obstruction effects of immobilized H2O layers near the clay surfaces are important in restricting the self-diffusion of unbound H2O in water-rich smectite gels.

Layered double hydroxides (LDHs) are layered ion exchangers, with a large surface-charge density, which react easily with organic anions. Various types of organics are rapidly substituted in the interlayer space of inorganic precursor LDHs. ZnAl-LDHs were intercalated with 1- to 19-carbon monocarboxylic acid anions by anion exchange of NO3-saturated LDH precursor phases in order to study the dependence of exchange reactions on synthesis parameters (temperature, pH, and interlayer anion). The carboxylic acid anion-LDHs synthesized were characterized using X-ray diffraction, infrared spectroscopy, thermal analysis, scanning electron microscopy, chemical analysis, and N2 adsorption. Carboxylic anion quantities in excess of the LDH anion exchange capacity easily replaced exchangeable nitrate anions at moderate pH. The intercalated LDH interlayer space depended on the alkyl chain length and orientation (inclination angle) of thecarboxylic-acid anion. Thelatticeparameter c0 ranged from 3.4 to 13.5 nm, but the a0 lattice parameter remained constant at 0.31 nm. Crystallographic analyses indicated a monomolecular arrangement of intercalated short-chain fatty-acid anions. At pH < 7, intercalated long-chain carboxylates showed a preferred bimolecular interlayer orientation. Carboxylic-acid anion exchange with LDHs at pH 7 resulted in the formation of two different sets of basal spacings, which indicated the coexistence of LDHs intercalated with monomolecular and bimolecular arrangements of interlayer carboxylic compounds.

Thermal treatment of the carboxylic acid anion-intercalated LDHs indicated stability up to ~140ºC. The release of interlayer water led to distortion of the crystallographic units and resulted in smaller basal spacings without collapse of the layered structure. Heat treatment re-oriented alkyl-chain carbon carboxylates (with >10 carbons) to a more upright interlayer position.

A clay-rich Callovo-Oxfordian sedimentary formation was selected in the eastern Paris Basin (MHM site) to host an underground laboratory dedicated to the assessment of nuclear waste-disposal feasibility in deep geological formations. As described initially, this formation shows a mineralogical transition from an illite-smectite (I–S) mixed-layered mineral (MLM), which is essentially smectitic and randomly interstratified (R = 0) in the top part of the series to a more illitic, ordered (R ⩾ 1) I–S in its deeper part.

This description has been challenged by using the multi-specimen method developed by Drits et al. (1997a) and Sakharov et al. (1999). It is shown that all samples contain a physical mixture of an unusually (?) illitic (∼65% I) randomly interstratified I-Exp (illite-expandable MLM) and of a discrete smectite, in addition to discrete illite, kaolinite and chlorite. Structural parameters of the different clay phases vary little throughout the series. According to the proposed model, the mineralogical transition corresponds to the disappearance of smectite with increasing burial depth.

Comparison with clay minerals from formations of similar age (Oxfordian-Toarcian) throughout the Paris Basin shows that the clay mineralogy in the deeper part of the series originates from a smectite-to-illite transition resulting from a low-temperature burial diagenesis. The anomalous lack of evolution of clay minerals in the upper part of the series is thought to be related to specific interactions between organic matter and clay minerals.

The sedimentology and mineralogy of a 2.5 m core from a palygorskite deposit of the Miocene Hawthorne Formation, southern Georgia is described. The lithology involves laminated clay-rich sediment composed of ∼90% clay and 10% sand, with six clay-pebble layers present. Sand to pebble-size clasts of phosphate material are common throughout the core. The sand laminations are probably flood-related and the clay-pebble layers are storm deposits, with the pebbles being derived locally from subaerial environments. Phosphate clasts are reworked bone material.

The sands are quartz-rich and are subarkosic in composition with average quartz counts of 86.50% and average total feldspar counts of 11.50%. Heavy minerals observed include orthopyroxene, clinopyroxene, amphibole, zircon, rutile, garnet, tourmaline, kyanite, muscovite, biotite, spinels and opaques. Palygorskite fibers dominate the clay-size fraction of the samples and comprise ∼80–90% of sample material with smectite comprising the remainder. Hydroxylapatite comprises ∼3% of sediment volume and occurs as individual euhedral hexagonal crystals and as clusters of crystals.

Investigation of this core suggests that the palygorskite deposit represents a dynamic system with regular flooding and storm deposition being common. Mineral composition of sands may be useful for stratigraphic correlation of palygorskite deposits in the Apalachicola Embayment. This study supports the general environmental interpretations of previous workers for the palygorskite deposits of southern Georgia, but provides greater detail.

Rb-Sr and oxygen isotope studies, in addition to K-Ar isotopic determinations published previously, are reported on diagenetic and hydrothermal fundamental particles (particle thickness of 0.03 to 0.05 nm and particle ab size of 0.02–0.05 µm) of the East-Slovak Basin. The combined data set allows us to ascertain the crystallization conditions of the illite material from two bentonite units collected at two basinal sites located ~20 km apart, and characterized by prolonged diagenetic conditions induced by progressive burial. A bentonite rock characterized by a short hydrothermal event from the Zempleni mountains to the SW of the East-Slovak basin is also studied.

For the two first sites, the δ18O values increase in one case and decrease in the other, when the size of the diagenetic fundamental particles from bentonite samples increases. These variations suggest that temperature increased in one and decreased in the second of the two samples collected in the basin, while the particles were growing. In the case of the hydrothermal bentonite, the δ18O values of the different size-fractions consisting of fundamental particles remain about constant, suggesting constant temperature and fluid chemistry.

The Rb-Sr dates of the fundamental particles of the three bentonite rocks were systematically higher than the corresponding K-Ar ages. The 87Sr/86Sr ratios, which are initially involved in the particle nucleation, appeared higher than that of contemporaneous sea-water. In all cases, the initial 87Sr/ 86Sr ratio decreases when particle size increases, which implies supply of external Sr into the bentonite units. This external Sr seems to have had an 87Sr/86Sr ratio close or identical to that of the contemporaneous sea water. This means that Sr, probably of sea-water origin, progressively diffused from host shales into the bentonite units, during burial diagenesis. In turn it favors the suggestion made previously about diffusion of K from shales into the bentonite layers during illitization of the smectite from these units.

Dioctahedral and trioctahedral smectites of very low Fe contents were exchanged with Ca (0.8 N CaCl2) and then with Cd (0.004–0.2 N CdCl2), resulting in the approximate Ca/Cd interlayer compositions 100/0, 75/25, 50/50 and 0/100. The samples were analyzed using 113Cd and 1H MAS NMR spectroscopy, at different hydration states, and by FTIR using films oriented at 90 and 45° to the infrared beam. When adsorbed from low-concentration CdCl2 solutions, as in this study, Cd is in the smectite interlayer as Cd2+, surrounded by water molecules. In smectite specimens with no tetrahedral charge, Cd occupies one single site in the center of the interlayer along the c axis but in smectite with tetrahedral charge, the basal oxygen atoms with excess negative charge interact with some of the Cd atoms more strongly, generating a second site in which Cd is displaced from the center of the interlayer and closer to those oxygen atoms. The 1H NMR study showed protons from hydration water and smectite hydroxyls and showed that both have more than one component. The FTIR and 1H NMR experiments indicate that Cd interacts with hydroxyl groups through one of the solvating water molecules in the first coordination sphere. Cadmium retains water molecules bridging Cd and OH groups even at low hydration states. Comparison with previous studies shows that, when adsorbed from high-concentration CdCl2 solutions, Cd species other than Cd2+ are present in sufficient quantities to enter the interlayer and create a different Cd-water complex, seemingly displacing Cd2+ from the center of the interlayer.

The controlled chemical oxidative polymerization of metanilic anion $(m{\text{-NH}}_2{\text{C}}_6{\text{H}}_4{\text{SO}}_3^{-})$$(m{\rm{ - N}}{{\rm{H}}_2}{{\rm{C}}_6}{{\rm{H}}_4}{\rm{SO}}_3^ - )$ within the interlayer of NiAl layered double hydroxide was performed using, for the first time, ammonium persulfate as the oxidizing agent. The quantity of oxidizing agent required for control of the interlayer polymerization was investigated systematically and it was found that interleaved polyaniline sulfonic (PANIS) was present in different oxidation states and protonation levels when different quantities of external oxidizing agents were added. A mechanism for the oxidative polymerization of metanilic anion in NiAl layered double hydroxide is proposed, based on the intercalation of the oxidizing agent and the interlayer polymerization of monomer. The resulting PANIS/NiAl LDH composites were characterized by powder X-ray diffraction, ultraviolet-visible absorption spectra, Fourier transform infrared and X-ray photoelectron spectroscopy.

Beidellites may exist on Mars and represent intermediate alteration products; their presence would indicate different alteration environments than previously identified because montmorillonite is a low-grade alteration mineral whereas beidellite is a higher-temperature alteration mineral, and often represents a step toward illite formation. The reflectance spectra of beidellites are under study to support their orbital detection on Mars, where spectral signatures of other Al-rich phyllosilicates have been observed. Reflectance spectra of ten Al-rich smectites are presented here which include pure beidellites and Al smectites having compositions between those of beidellite and montmorillonite, and emphasis is placed here on the OH combination bands near 4545 cm−1 (2.2 μm) as these vibrational features are commonly used in the identification of phyllosilicates on Mars. Shifts were observed in the Al2OH band centers, which occur near 4590 cm−1 (2.18 μm) in reflectance spectra of beidellite and near 4525 cm−1 (2.21 μm) in reflectance spectra of montmorillonite. These are compared with the Al2OH bending vibrations observed near 941–948 cm−1 (10.5–10.6 μm) for beidellite and near 918–926 cm−1 (10.8–10.9 μm) for montmorillonite. Although the octahedral site cation composition provides the greatest influence on the vibrational energies of the M2OH groups, the tetrahedral site cation composition also influences these vibrations. Shifts were observed in the Si-O-Al bending vibrations from 552 and 480 cm−1 (18.1 and 20.8 μm) in beidellite spectra to 544 and 475 cm−1 (18.4 and 21.0 μm) in montmorillonite spectra. Gaussian modeling of the 4545 cm−1 (2.2 μm) bands led to the discrimination of four overlapping bands in each of the ten Al smectite spectra examined in this study. Shifts in the band center and area of the primary spectral band are coordinated with substitution of Al for Si in the tetrahedral sheet. This is consistent with beidellites having a greater tetrahedral layer charge than montmorillonites. The observed spectral differences were sufficiently large that these Al-rich smectites can be differentiated in orbital data of Mars. A pure beidellite-type spectrum is observed in an isolated Al phyllosilicate-bearing outcrop in Libya Montes, a region where Fe-rich smectite is common but Al-rich smectite is rare. Beidellite-type reflectance spectra were also observed in one area of the Nili Fossae region. In contrast, a variety of Al phyllosilicates were found in the ancient rocks at Mawrth Vallis, including some smaller clay-bearing regions exhibiting spectral signatures more consistent with beidellite-like than montmorillonite-like chemistry.