The boiling 5-M-NaOH treatment was found to aid in the identification and characterization of goethite and hematite by effectively concentrating the two Fe oxides in kaolinitic-gibbsitic soil clays. No transformations of goethite to hematite or hematite to goethite were detected, but poorly crystalline, highly Al-substituted goethite was found to dissolve and recrystallize into a more well-crystalline, less Al-substituted goethite in samples low in Si. The Si released from kaolinite was sufficient to block goethite dissolution and recrystallization in kaolinitic samples, but noncrystalline silica had to be added to samples rich in gibbsite to minimize this effect.

This contribution focuses on the abatement with hydrogen of CO2 and non-CO2 emissions. It is agenda-setting in two respects. Firstly, it challenges the globally accepted hydrocarbon sustainable aviation fuel (SAF) pathway to sustainability and recommends that our industry accelerates along the hydrogen pathway to ‘green’ aviation. Secondly, it reports a philosophical and analytical investigation of appropriate accuracy on abatement strategies for nitrogen oxides and contrails of large hydrogen airliners. For the second contribution, a comparison is made of nitrogen oxide emissions and contrail avoidance options of two hydrogen airliners and a conventional airliner of similar passenger capacity. The hydrogen aircraft are representative of the first and second innovation waves where the main difference is the weight of the hydrogen tanks. Flights of 1000, 2000, 4000 and 8000 nautical miles are explored. Cranfield’s state of the art simulators for propulsion system integration and gas turbine performance (Orion and Turbomatch) were used for this. There are two primary contributions to knowledge. The first is a new set of questions to be asked of SAF and hydrogen decarbonising features. The second is the quantification of the benefits from hydrogen on non-CO2 emissions. For the second generation of long-range hydrogen-fuelled aircraft having gas turbine propulsion, lighter tanks (needing less thrust and lower gas temperatures) are anticipated to reduce NOx emissions by over 20%; in the case of contrails, the preliminary findings indicate that regardless of the fuel, contrails could largely be avoided with fuel-burn penalties of a few per cent. Mitigating action is only needed for a small fraction of flights. For conventional aircraft this penalty results in more CO2, while for hydrogen aircraft the additional emission is water vapour. The conclusion is that our research community should continue to consider hydrogen as the key ‘greening’ option for aviation, notwithstanding the very significant costs of transition.

The adsorption from chloroform solution of the herbicide diclofop, (RS)-2-(4-(2,4-dichlorophenoxy)phenoxy)propionic acid, and its methyl ester diclofop-methyl on Cu2+-, Al3+-, and Fe3+-exchanged bentonite samples was investigated. For comparison, the complexes formed by diclofop were synthesized and studied. Diclofop adsorbed on the clays and formed carboxylate bonds to the interlayer ions. Diclofop-methyl also adsorbed, but its interaction involved the formation of hydrogen bonds with water molecules in the interlayer. Traces of diclofop were observed in both the solution and the clays after adsorption of diclofop-methyl, indicating that some hydrolysis of the ester to the corresponding acid occurred. Thus, pesticides forming neutral complexes with interlayer cations in montmorillonite in soils may be extractable by solvents and therefore released into the environment.

X-ray diffraction, infrared, and cation-exchange capacity measurements of the reaction products of montmorillonites with YbCl3.6H2O show that at 1 atm irreversible sorption of Yb3+ increases with increasing temperature in the range 20° to 280°C, whereas at 110 atm it decreases with increasing temperature. Above 100°C, less irreversible sorption occurs at 110 atm than at 1 atm. The decreased sorption at high pressure is attributed to reduced cation hydrolytic fixation and to rapid expulsion of interlayer Yb3+ by interlayer water at higher temperatures, with a concomitant decrease in Yb3+ migration to octahedral sites. At 110 atm, 160° and 200°C treatments cause changes in infrared absorption bands (884 cm-1, 848 cm-1) suggesting that sorbed Yb3+ is charge compensated by the deprotonation of Fe3+- and Mg2+-hydroxyl groups. At 290°C deprotonation is restricted to Fe3+-hydroxyl groups.

The sorption properties of Co, Cu, Ni, and Ca were studied in a mixed mineral suspension of synthetic MnO2 and Wyoming montmorillonite. The distribution of the sorbed cations between the two solid phases was measured by indirect chemical fractionation with acidified NH2OH-HCl and by direct X-ray spectroscopic analysis of mineral particles using electron microscopy. Electron microscope and NH2OH-HCl measurements of the quantity of Co sorbed on MnO2 agreed within 6%. Seventy-seven, 67, and 69% of the total Co, Cu, and Ni sorbed by the mixed mineral suspension was found on the manganese oxide. The opposite distribution was found for sorbed Ca with 28% on the manganese oxide and 72% on the montmorillonite particles. The observed differences in metal sorption by these minerals are related to the cation-sorption mechanisms of manganese oxide and montmorillonite.

If we return to the experiences of our youth, we perceive what had the power to awaken our curiosity and ambitions*. The non-conformism of the Surrealists was fostered by Romantic sources and every conceivable symbolism; even if in a roundabout manner, it was through them that the names of Klee and Kandinsky were first heard. The world of the marvellous, the only one decreed worthy of attention, opened out onto painting. The moderns of the group: Dali, Tanguy, Masson, received first prize for poetic adventure, but they harked back to certain selected precursors—rightly or wrongly—for the same gifts that they had themselves: Uccello, Bosch, Dürer, Blake, and Gustave Moreau. And indeed, by retaining only the unexpected, the fantastic, and (often indulgently) the scandalous, a taste was maintained for emotional shock and association, as exemplified by the sustained style of André Breton, and the more supple prose of Aragon.

Clayey sediments of marine origin having sensitivities (ratio of undisturbed to remolded shear strength) as high as 1000 at a reduced salt concentration are found around Ariake Bay, Kyushu, Japan. The clay fraction of the sediments contains smectite as a principal mineral (33–42%) in contrast to the illitic composition of most previously described quick-clays. However, this smectite is a low-swelling type, and the Na-form expands only to about the same extent as the Ca-form and gives a sediment volume almost equal to that of the Ca-clay. This low-swelling smectite appears to consist of packets of unit layers even after saturation with Na, and thus reacts like the kaolinite or illite of conventional quick-clays.

The purpose of this paper is to present a commentary on the current state of contemporary African philosophy and to offer some criticisms and recommendations. The question concerning African philosophy has been debated for some years now and one has witnessed a number of interesting works on this topic.

Many things have passed as money: salt in Abyssinia, tea-bricks in Asia, sugar in the West Indies, barrels of oil in Texas … and metals everywhere. The list seems endless. However, as transactions increased, wealth accumulated, and states levied taxes, such proto-moneys moved from the simple “double coincidence of wants” into more rational and complex forms. They catered for a market or hierarchy of markets. “Money,” said Carl Menger, “is not a political invention.”

Montmorillonites saturated with Al3+, H+-Al3+, and K+ were titrated in H2O, acetonitrile (AN), and dimethylformamide (DMF) to investigate the acidic properties of the clay in these solvents and to evaluate the application of nonaqueous titration procedures for studies of the acidic properties of 2:1 swelling clays. Samples were titrated with tetramethylammonium hydroxide using a combination glass electrode for Potentiometric determination. Titers of base required to reach the final Potentiometric endpoints were greater in AN than in DMF and H2O. The larger titers in AN compared to H2O were attributed to pH-dependent sites for which an inflection was not observed in the latter solvent. Titration curves of Al-saturated montmorillonite in AN showed evidence of a salt-induced hydrolysis which was confirmed by titration curves of salt extracts. The hydrolysis reaction was more evident in AN than in H2O and was probably due to a disruption of the H2O structure by AN and a polarization of the H2O of solvation. The hydrolysis reaction was enhanced in the presence of excess salt due to the ion exchange of H+ from the exchange surface. These studies indicate that acidic properties of clays may be drastically altered in organic solvents. The acidic properties may be used to advantage, for example, in the determination of edge-site acidity. In addition, they have implications concerning possible chemical reactions and/or alterations of clay in organic solvents.

It is with these virile words of the Martinique poet Aimé Сésaire, an expression of assurance regained, testimony to a self-confidence once stolen but then reconquered, that I would like to open my remarks.*

Africa was present at the last great international philosophical meeting two years ago in Montreal. I would like here to illustrate the meaning behind this presence and to explain the reasons why we wanted to be present, in order to avoid facile misunderstandings which could have weighty consequences.

A new approach to the interpretation of Mössbauer spectra of Fe3+-phyllosilicates having vacant trans-octahedra is based on (1) crystal structure simulation methods that allow for the size and the shape of a Fe3+-octahedron as a function of the nearest surrounding cations; and (2) calculations of electric field gradients (EFG) on Fe3+ in terms of the ionic point-charge model. Calculations were performed by direct summation within the region of radius ≤50 Å. Coordinates for the anions in the coordination octahedra have been assigned to take into account the nearest cationic environment. Atomic coordinates for the rest of the summation volume are those for the average unit cell. EFG calculations for cation combinations responsible for the visible quadrupole splitting Δvis in the spectra of nontronite, “red” muscovite, and celadonite have led to good agreement between Δvis and Δcalc. Computer fitting of the nontronite and celadonite spectra based on EFG calculations for the rest of the possible cation combinations suggests that the distribution of tetrahedral cations in nontronite obeys the Loewenstein rule, and in celadonite, the distribution of R3+ and R2+ over cis-octahedra is predominantly ordered, in agreement with electron diffraction and infrared spectroscopy data. The Mössbauer spectrum of one of the glauconites suggested the presence of celadonite-like and muscovite-like domains in its 2:1 layers.

The oxidation of 1,2- and 1,4-dihydroxybenzenes (1,2-DHB and 1,4-DHB) by unbuffered aerated suspensions of synthetic bimessite was studied by continuously monitoring the H+, Mn2+, dissolved O2, and organic radical concentration of the aqueous phase during the reaction. The reaction rapidly generated a very high pH, attributed to oxide dissolution, and the alkaline conditions prevented Mn2+ release into solution over the entire reaction period. Semiquinone radical anions accumulated early in the reaction and then diminished. A secondary radical product appeared in solution during the reaction of the oxide with 1,2-DHB, and was tentatively identified as an hydroxylated semiquinone. The oxide/DHB ratio controlled the maximum concentration and persistence of these radicals in solution as well as the degree to which O2 was consumed as an electron donor. In general, low oxide/DHB ratios promoted O2 uptake by the system, consistent with the subordinate role of O2 as a competing electron acceptor in the presence of excess Mn oxide. Soluble phosphate suppressed O2 consumption, but the mechanism by which it interacted with the reaction system was not determined.

The heterogeneity of sites for Ca→K exchange was examined by microcalorimetry in the <0.2-μm fractions of some selected smectites. Six groups of sites, ranging in exothermic exchange enthalpy (-d(ΔHx)/dx) from 5.7 to 10.9 kJ/eq were identified. In Wyoming bentonites, only three groups with enthalpies of 5.7 to 7.5 kJ/eq were distinguished, although in the 0.2-1.0-μm fraction, a 10.7-kJ/eq group was also observed. Redhill and Camp Berteau smectites contained, in addition, groups with enthalpies of 8.7-10.9 kJ/eq, but a New Mexico sample only had groups with the higher values. Thus, the exchange enthalpies of four main groups of sites (reclassified from those observed) appear to be inversely related to the extents of interlayer expansion in the samples by the adsorption of polar molecules. Consequently, a 'true mont-morillonite,’ such as a <0.2-μm Wyoming bentonite, contains only fully expanding layers with -d(ΔHx)/ dx values between 5.7 and 7.5 kJ/eq. As such, it is less heterogeneous and should have a much greater swelling capability than Camp Berteau montmorillonite which has, in addition, groups with exchange enthalpies of 8.7 and 10.3 kJ/eq.

Emile Benvcniste may be used to introduce the topic. The French linguist begins an essay on “Euphemisms Ancient and Modern” with a paradox about the early Greek definitions of euphemism. “To speak words which augur well” is one meaning given, but another is “to maintain silence”. This initial contradiction is further compounded by yet a third expression, “to shout in triumph”. The dilemma is, however, easily dissolved. To speak words which augur well implies, for special occasions, an exhortation even to shout triumphantly, “to assent by an, auspicious outcry”: it further implies, again depending on the circumstances, “to avoid words which augur ill”, hence, if necessary, to say nothing. As one definition explains “avoid all unlucky words during sacred rites: hence, as the surest mode of avoiding them, keep a religious silence” (original emphasis). Paradox terminates; we are merely dealing with “a euphemism for a euphemism” taking an expression of Benveniste out of context.

The effect of electrolyte concentration, exchangeable sodium percentage (ESP), sodium adsorption ratio (SAR), and pH on the flocculation-dispersion behavior of 50/50 mixtures of reference illite with reference kaolinite or reference montmorillonite was investigated. The clays were Na- or Ca-saturated and freeze-dried before use. Critical coagulation concentrations (CCCs) were investigated in the range of pH 5.9 to 9.6, percent Na-clay 0, 10, 20, 40, 60, 80, and 100 and SAR 0, 10, 20, 40, 60, 80, and ∞. CCC values increased with increasing ESP, increasing SAR, and increasing pH. The pH dependence of illite/kaolinite was greater than that of illite/montmorillonite especially at high ESP and SAR. The presence of illite did not play a dominant role in determining flocculation-dispersion behavior of the 50/50 clay mixtures. The CCCs of illite/kaolinite resembled reference illite more than reference kaolinite for SAR 0 to SAR 60. Illite/montmorillonite exhibited CCCs more similar to reference illite than reference montmorillonite at SAR 40 and SAR 60. At the agriculturally desirable ESP and SAR values of 0 to 15, all the 2:1 clays and 2:1 clay mixtures demonstrated similar CCC values.

The negative surface charge of synthetic allophanes with a range of Si/Al ratios decreased and positive charge increased with increasing alumina content at a given pH. The phosphate adsorption capacity also increased with increasing Al content. That this relationship between composition and chemical reactivity was not found for the soil allophanes is attributed to the presence of specifically adsorbed organic or inorganic anions on the natural material. Both synthetic and natural imogolites had a much lower capacity to adsorb phosphate than the allophanes and adsorbed anomalously high amounts of Cl− and ClO4− at high pH. It is proposed that intercalation of salt occurs in imogolite, although electron spin resonance studies using spin probes failed to reveal the trapping of small organic molecules in imogolite tubes. These spin probes in the carboxylated form did, however, suggest an electrostatic retention of carboxylate by imogolite and a more specific adsorption by allophane involving ligand exchange of surface hydroxyl. The results illustrate the inherent differences in charge and surface properties of allophane and imogolite despite the common structural unit which the two minerals incorporate.