The adsorption of Cu2+ on microcrystalline gibbsite and boehmite from aqueous solutions having 2/1 and 5/1 glycine/Cu ratios has been studied using electron spin resonance (ESR). The presence of glycine inhibited metal adsorption on gibbsite above pH 5, apparently by reducing Cu hydrolysis. The preferred adsorbed species on gibbsite and boehmite, based upon the ESR parameters, were probably Cu(gly)+ and Cu(gly)20, respectively. In both experiments, rigidly-bound ternary complexes formed with Cu2+ simultaneously bonding to the surface and one or more ligands. A large excess of glycine destabilized the ternary complex and caused the desorption of Cu2+. The preferred orientation of the Cu complex on gibbsite suggests that the adsorption occurred at crystal steps and that the glycine molecule hydrogen bonded to hydroxyls of the (001) surface.

The surface free energy components of clay-organic complexes were determined to assess to what extent an organic adsorbate modified the surface properties of the mineral, insofar as the stability of soil aggregates is concerned. Adsorption isotherms for two synthetic, humic acid-like polymers were determined on a Ca-montmorillonite. From contact-angle measurements performed on dry surfaces, the surface free energy properties of the clay-organic complexes were determined using the two-liquid-phases method (water and hydrocarbons). This method allows both the dispersive and nondispersive components of the solid surface free energy, γDS and γPS, to be determined. The results show that a very small amount of polymer (1% by weight) adsorbed on the external surfaces of the montmorillonite decreased markedly the surface free energy components of the clay: γDS decreased from 75 to 28 mJ/m2 for polycondensate catechol (PC) and from 75 to 30 mJ/m2 for polycondensate catechol triglycine (PCT), whereas γPS ranged from 35 to 16 mJ/m2 (PC) and from 35 to 17 mJ/m2 (PCT). Although their chemical compositions were different, both polymers similarly modified γDS and γPS. Increasing the amount of polymer adsorbed (from 1% to 3.5% by weight) affected mostly γPS, which became as low as 5 mJ/m2; meanwhile, γDS decreased from 30 to 23 mJ/m2. Possibly, the molecular orientation of the adsorbate changed in the process of dehydration. Following adsorption of synthetic humic acid-like polymers, dry Ca-montmorillonite complexes displayed γS values < 50 mJ/m2, which were consistent with the solid-water contact angles measured in air.

We show that trade credit contracts between sectors can provide a useful alternative to fiscal transfers during a major productivity shock. Defaults in credit contracts function as transfers between sectors, which can be implemented through a bankruptcy law or through credit renegotiation. Transfers implemented through defaults allow for a reduction in the size of the fiscal policy that restores the economy to the optimal allocation, constituting a relevant alternative to economies without an available fiscal space to implement the optimal policy.

In a study of “rana” soils of central Spain, hydroxy-interlayered 2:1 clay minerals were identified in the upper horizons and high-charge smectite in the lower horizons, with kaolinite the most abundant phyllosilicate. The high-charge smectite showed a basal spacing of 18 Å on Mg-saturation and glycerol solvation and 10 Å on K-saturation and air-drying. It is concentrated in the coarse fractions and appears to be basically a beidellite in the fine-silt fractions and a montmorillonite in the clay fractions. Pre-existing illite was probably transformed into hydroxy-interlayered 2:1 clays in the surface horizons, whereas high-charge smectite formed in the deeper horizons. These minerals, which were apparently not stable in the existing soil conditions, were the first stage in the degradation process of illite. The stable mineral in these soil profiles was kaolinite.

This paper compares the texture of palygorskite after acid leaching with that of the product after extraction silica is removed. These effects were evaluated on the basis of nitrogen adsorption-desorption and mercury penetration porosimetry. Acid leaching at reflux temperature with 2 N HCl resulted in an increase in surface area from 138 to 399 m2/g, due to a partial (~50%) dissolution of the octahedral sheet and the creation of microporosity. This microporosity disappeared if the silica generated by the leaching was removed. The surface area also decreased from 399 to 214 m2/g, and the pore volume decreased from 0.538 to 0.507 cm3/g. The microporosity must therefore have been due to texture development in the generated silica.

The structural damage produced by dry grinding and acid leaching of chrysotile was studied by transmission and scanning electron microscopy, infrared spectroscopy, X-ray powder diffraction, and thermogravimetric analysis. Severe dry grinding converted the chrysotile fibers into fragments having strong potential basic reaction sites. These sites were immediately neutralized by molecules present in the atmosphere (e.g., H2O, CO2). Acid leaching transformed the chrysotile fibers into very porous, non-crystalline silica, which was easily fractured into short fragments. The damage produced in the chrysotile structure by grinding or leaching was assessed by monitoring the intensity of various infrared absorption bands.

Al-rich di, trioctahedral chlorite exists as the species cookeite and sudoite. Di,dioctahedral chlorite exists as the species donbassite. Cookeite has essential Li in its structure, sudoite has essential Mg, and donbassite has only small amounts of either element. To date, sudoite has been reported to have only IIb structural units and donbassite to have only Ia structural units. Cookeite is based primarily on Ia structural units, but IIb units are present in specimens from two localities. Most Al-rich chlorite species have regular-stacking “r” or “s” 2-layer stacking sequences, but 1-layer Ia-2 and Ia-6 polytypes also are known. The structural units (Ia or IIb) and the specific stacking sequences can be explained by a combination of local charge balance and minimization of cation-cation repulsion involving the interlayer and tetrahedral cations. X-ray powder diffraction data are adequate to differentiate Al-rich chlorite from trioctahedral chlorite and to identify the type of structural unit present, but single crystal study is necessary to identify the 2-layer and 1-layer sequences with certainty.

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

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

The adsorption of tris(1,10-phenanthroline)-ruthenium(II) (Ru(phen)32+) by two kinds of colloidally dispersed clays, sodium montmorillonite and synthetic saponite, was studied by spectrophotometric and electron-optical methods. Montmorillonite adsorbed this complex stronger than saponite. The electronic spectrum measurements suggested that the electronic states of the complex were more perturbed on adsorption by montmorillonite than by saponite. High-performance liquid chromatography was attempted on an ion-exchanged adduct of optically active Ru(phen)32+ and these clays. 1,1′-Binaphthol was eluted with a 1:1 (v/v) water-methanol mixture as an eluent. The compound was resolved with a separation factor of 15 and 1.4 on the saponite and montmorillonite columns, respectively. If tris(acetylacetonato)-chromium(III) was eluted with water, the compound was resolved with separation factors of 1.9 and 11 on the saponite and montmorillonite columns, respectively. These separation tendencies were probably due to the difference in the external surface area and the density of the bound chelates.

Infrared spectra of adsorbed pyridine have been used to obtain qualitative information on the nature of the interaction of pyridine with different rhodium catalysts supported on palygorskite and silica. Based on these data, qualitative definitions of the adsorption sites of these catalysts have been deduced. The catalysts were prepared with natural palygorskite, and palygorskite dehydrated in vacuo at 150°C and 400°C. In this way, catalysts were obtained that had different water contents and, therefore, different acidities. Lewis-bound pyridine was detected by infrared spectroscopy from room temperature to 500°C. The greatest acidity was found in a catalyst prepared with the palygorskite support dehydrated at 150°C before preparation of the catalyst. With this catalyst, strongly hydrogen-bound pyridine was observed when evacuation was carried out at temperatures between 150°C and 300°C. Catalysts prepared with the palygorskite support pretreated at 400°C did not exhibit strongly hydrogen-bound pyridine, and Lewis acidity decreased significantly. As expected, hydrogen-bound pyridine was also detected for rhodium supported on silica. However, it was desorbed at temperatures below 150°C. The results of the acidity studies follow the same pattern as those for 1 -hexene double-bond migration under hydrogénation reaction conditions.

An end-member natroalunite of composition (K0.04Na0.96)(Al2.98Fe0.02)(SO4)2(OH)6 occurs in saprolitic clays in a laterite profile developed over Deccan Trap basalts at Matanumad in the Kutch region of Gujarath state, India. Pseudocubic natroalunite crystals, ranging from 0.5 to 1 µm in size, have replaced pseudohexagonal, 2-µm-size platelets of kaolinite. The reverse reaction (kaolinization of natroalunite) has also been observed in the laterites and bauxites immediately adjacent to the saprolite. The kaolinite crystallites that replaced natroalunite occur as a mosaic of anhedral platelets that range in size from 0.1 to 0.3 µm. The formation of natroalunite at Matanumad postdates the laterization of the basalts. It is related to the post-diagenetic formation of sulfuric acid-rich solutions by the oxidation of pyrite in the Eocene-Oligocene black shales of the Matanumad basin. The kaolinitic clays at the top of the saprolite zone have been intensely altered by the acidic solutions, leading to a high concentration of natroalunite.

On the basis of progressive acid dissolution the Thompson-Hower model states that mixed-layer glauconite/smectite and illite/smectite contain potassium in two structural sites: a mica-type K position (site 1) and a position of uncertain structural status more prone to dissolution (site 2). Site 2 was thought not to retain radiogenic argon (40Ar*). Using extensive progressive acid dissolution and K/Ar studies on a sized illite/smectite (I/S), determining the amount of K in site 2 is shown to be somewhat more complicated than previously thought because the dissolution pattern depends on acid normality. More important, site 2 fully retains 40Ar*, and no age correction is thus necessary as is required by the Thompson-Hower model, further affirming the geochronologic value of illite in mixed-layer clay. These data are also relevant to understanding the crystal and particle structure of I/S. Site 2 is probably a partly filled K interlayer that develops as an intermediate kinematic step on the way to being fully filled during the transformation of smectite to illite.

Polynuclear hydroxy-Al cations were prepared by partially neutralizing dilute solutions of aluminum chloride. These cations were introduced in the interlayer space of montmorillonite by cation exchange, which formed heat-stable pillars between the silicate layers. Polynuclear hydroxy-Al was preferentially adsorbed on montmorillonite compared with monomer-Al; the maximum amount adsorbed was ∼400 meq/100 g of montmorillonite. Of this amount 320 meq was non-exchangeable. The 001 X-ray powder diffraction reflection of the polynuclear hydroxy-Al-montmorillonite complex was at 27 Å, with four additional higher-order basal reflections, giving an average d(001) value of 28.4 Å. This complex was thermally stable to 700°C. An analysis of the basal reflections by the Fourier transform method indicated that the 28-Å complex had a relatively regular interstratified structure of 9.6- and 18.9-Å component layers with a mixing ratio of 0.46:0.54. This ratio implies that the hydroxy-Al pillars occupied every second layer. Considering the relatively small amount of Al adsorbed and the thermally stable nature of the structure, the hydroxy-Al pillars must have been sparsely but homogeneously distributed in the interlayer space.

The morphological characteristics of starch granules preserved on ancient ground stone tools can reveal which plant species were processed and consumed and even infer tool function. Bedrock metates are commonly associated with the processing of localized seasonal resources, providing potential evidence for past human lifeways, including foods collected and processed, social gatherings, settlement patterns, land investment, and territorial behavior. In contrast to ground stone artifacts preserved in a buried context that have been studied extensively, limited starch research has been conducted on the potential for environmental contamination of open-air bedrock mortars and metates exposed to natural erosional elements. This project examines the residue samples of bedrock metates from three archaeological sites in southern Oregon in the United States to compare the starch yields of extraneous material cleaned from the grinding surface to those extracted from interstitial matrices deeper within the bedrock. Significantly greater number of starch granules were recovered from deep within the cracks and crevices than from the surface. Our study suggests that environmental contamination can be managed if separate surface and control samples are collected and analyzed in conjunction with the interstitial samples. Examining the potential for environmental contamination on exposed grinding surfaces is crucial for confidence in starch granule results and improving our understanding of human dietary behavior.

Alteration products of andesite cobbles from wet soils formed in volcanic colluvial material were studied using petrographic, electron microscope, X-ray powder diffraction, and thermal techniques. Augite phenocrysts altered by congruent dissolution leaving voids which were subsequently filled with smectite. Plagioclase also altered to produce micrometer-size spheroidal aggregates of smectite. Halloysite was not observed within the altered cobbles, although it was abundant in the soil matrix. The formation of smectite in the altered cobbles was probably favored by the restrictive drainage of the microenvironment in combination with wet soil conditions.

This introduction to the special issue ‘Gender and Work in Twentieth-Century Italy’ draws on key strands of historical scholarship on gender and work, including women workers’ experiences, labour market discrimination, domestic work, the impact of gender norms, and ideas of masculinity and femininity on work identities. It traces the development of feminist influence within this scholarship, from making women workers’ experiences visible to challenging essentialist notions of gender identities. Drawing on post-structuralist and intersectional perspectives, particularly influenced by Joan Wallach Scott and Judith Butler, the scholarship on which this special issue is based understands gender as a system of power signified through language and social constructions, and builds on the critique of the dichotomies and essentialisations of traditional labour history, proposing a systemic and structural approach to understanding gendered experiences of work. By exploring the intersections of gender, work and power, this collection offers insights into wider European developments and challenges established historical concepts and narratives. It highlights the importance of understanding gender dynamics in shaping labour relations and social structures, ultimately contributing to a more nuanced understanding of labour and power dynamics in twentieth-century Italy and beyond.