Hectorite and saponite are exchanged with [Al13O4(OH)24(H2O)12]7+ and the amount of Al3+ adsorbed and Na+ released are followed as a function of the exchange conditions. On saponite the reaction is a pure ion exchange with 2–2.15 mmol Al3+/g adsorbed and release of 0.80 mmol Na+/g. On hectorite the ion exchange is accompanied by supplementary hydrolysis-polymerization of Al13. When excess Al is offered in the form of Al13, ion exchange is incomplete and is accompanied by precipitation and polymerization of Al13 on the surface of both hectorite and saponite. The typical spacing of 1.8 nm is developed after washing, when at least 1.3–1.4 mmol Al3+/g is adsorbed. Above a loading of 2.2–2.5 mmol/g the 1.8 nm spacing is obtained without washing. Only pillared saponite with a loading of at least 1.9 mmol Al3+/g is thermally stable up to 550°C.

An aluminous Ca-montmorillonite from southern Manitoba, Canada, has been shown to generate very low pH values in clay/groundwater slurries over a range of ionic strength of the groundwater (fresh and saline) and temperatures from 25°–90°C. Dialysis experiments as well as results of X-ray diffraction and FTIR vibration spectroscopy point to an acidification mechanism that involves hydrolysis of exchangeable Al3+ ions, thus releasing protons, and the subsequent intercalation of gibbsite-like hydroxy-Al complexes into the smectite lattice forming a non-expandable “Al”-montmorillonite.

Saponite, hectorite, and laponite have been pillared with cationic Al clusters, and special attention has been given to the solution chemistry or Al. Pillared saponite is obtained after exchange with refluxed Al solutions; while for hectorite, Al solutions treated with ammonium acetate give a pillared product with 1.8–1.9 nm spacing and thermal stability up to 873 K. In both types of solutions, the Keggin ion Al cluster is a minority species or totally absent. The typical 1.8–1.9 nm spacing is only obtained after washing. The quality of the pillared material can be judged from its thermal stability, its surface area, and the width of the d001 line before and after pillaring. The width should not exceed 0.3 nm before calcination and 0.5 nm after calcination. The latter criterion reflects the importance of the crystallinity of the parent clay for successful pillaring. Pillaring in concentrated conditions occurs by a combination of ion exchange and precipitation of Al and gives materials that exhibit poor thermal stability.

Coquimbite, AlFe3+3(SO4)6(H2O)12⋅6H2O, was considered as a pure Fe3+ hydrated sulfate. However, previous mineralogical studies pointed out the occurrence of essential Al, occupying a distinct site in the crystal structure of this mineral. Through the critical re-examination of the available literature and new crystal-chemical data collected on a specimen from the Monte Arsiccio mine, Apuan Alps, Tuscany, Italy, the chemical formula of coquimbite has been revised, taking into account the occurrence of Al. Coquimbite has a homeotypic relationship with paracoquimbite, Fe4(SO4)6(H2O)12⋅6H2O; both mineral species belong to the coquimbite group. On the contrary, aluminocoquimbite, Al2Fe2(SO4)6(H2O)12⋅6H2O, has a different topology and does not belong to that group.

Kaolinite and synthetic γ-Al(OH)3 (gibbsite or hydrargillite) were reacted with phenylphosphonic, phenylphosphinic and 2-nitrophenol-4-arsonic acids. The products were studied by powder X-ray diffraction, transmission electron microscopy/selected area electron diffraction/ energy dispersive X-ray/Fourier transform infrared and simultaneous thermogravimetric/differential thermal analysis. The acids were not intercalated but, instead, easily destroyed the structure of the minerals. Lamellar Al phenylphosphonate and aluminium phenylphosphinate and phenylarsonate with polymeric linear-chain structures were formed from kaolinite. The reaction between gibbsite and the same acids yielded almost identical products. No evidence of formation of grafted kaolinite derivatives after the reaction with phenylphosphonic acid was found.

Twenty nine Fe oxide concentrates of Thai soils formed on basalt, sandstone, shale/limestone and granite were investigated. Goethite and hematite are relatively more abundant in granitic and basaltic soils, respectively. Values of Feo/Fed range from 0.01 to 0.28 indicating that free Fe oxides are mostly crystalline.

There are no systematic differences in unit-cell dimensions for goethite and hematite in soils on different parent materials. Mean crystallite dimensions calculated from the 110 reflections are greater for hematite than for goethite. Aluminium substitution varies from 8 to 24 mole% for goethite and from 4 to 17 mole% for hematite. The dehydroxylation temperature for goethite ranges from 285ºC to 320ºC. The goethite in basaltic soils has a smaller crystal size and Al substitution, as well as a lower dehydroxylation temperature, compared to soils on other parent materials. The dehydroxylation temperature of goethite is positively related to Al substitution (R = +0.58), MCD110 (R = +0.49) and Ald (R = +0.53). The Mn, Ni, Cr, V and P in these soils occur in Fe oxides rather than as discrete minerals.

A synthetic analogue, Ca(Ti0.6Al0.2Ta0.16Nb0.04)OSiO4, of an aluminoan tantalian titanite previously described from Craveggia pegmatite (Piemonte, Italy) has been prepared by a ceramic synthesis technique and its crystal structure determined by Rietveld analysis of the powder X-ray diffraction pattern. The synthetic Al-Ta-Nb-rich titanite adopts space group A2/a implying that substitutions at the single octahedral site destroy the coherence of the off-centering of octahedral chains in the titanite structure resulting in a P 21/a → A2/a phase transition. Unit-cell dimensions obtained for the Al-Ta-Nb-rich titanite are: a = 7.0649(1) Å; b = 8.7187(1) Å; c = 6.5701(1) Å; β = 113.755(1)°, V = 370.41(1) Å3. The extensive replacement of Ti by Al, Ta and Nb results in a considerable decrease in the distortion of all coordination polyhedra in the structure of this titanite. These structural data suggest that a solid solution CaTi1-x(Alx /2 [Ta,Nb]x /2)OSiO4 (0 ≤ x ≤ 0.4) adopting the titanite structure might exist.

Warwickite constitutes about 5% of an outcrop of metamorphosed ultramafic rocks of Precambrian age in North-West Greenland. It occurs as slender grains, several millimetres long, and in anhedral grains up to 5 mm in size, together with forsterite, pleonaste, phlogopite, magnetite ± tourmaline. Post-metamorphic alteration of warwickite produced a network of boron-rich minerals and magnetite. The warwickite, containing up to 9.72% Al2O3, displays a significantly different chemical composition from warwickite elsewhere, such as that in recrystallized limestones from the type locality Warwick, New York, and in lamproitic and carbonatite-like rocks at Jumilla, Spain.

Euhedral crystals of complexly zoned niobian titanite (up to 0.3 mm) are enclosed in hedenbergite (Hd53—81Di15—43Jh3-5) and quartz from a hedenbergite vein skarn at Kamenne doly near Pisek, Czech Republic. They are associated with minor clinozoisite-epidote (Ps3—22), calcite, plagioclase (An95). scapolite (Me80—82), scheelite, pyrrhotite, fluorapatite, arsenopyrite, native bismuth and Bi,Te-minerals. The following textural and compositional subtypes were recognized: (I) Nb-rich titanite, (II) Nb-moderate titanite in the central zone, (III) Nb-poor, Sn-enriched titanite and (IV) Nb-poor, Al,F-rich titanite in the outer zone. The substitution Al(Nb,Ta)Ti—2 is dominant in subtypes I and II, the titanite subtype I being characterized by elevated contents of Al ≤ 0.257 atoms per formula unit (a.p.f.u.), Nb (≤ 0.161 a.p.f.u.) and Ta (≤ 0.037 a.p.f.u.). Amounts of Al, Nb and Ta in subtype II are smaller and more variable. The minor substitution SnTi—1 occurs chiefly in titanite subtype III with a content of Sn ≤ 0.039 a.p.f.u.. The substitution Al(F,OH)(TiO)_i is typical for titanite subtype IV exhibiting elevated contents of Al (s£ 0.221 a.p.f.u.), F (≤ 0.196 a.p.f.u.) and Fe (≤ 0.039 a.p.f.u.).

The negative relationship of substitutions Al(F,OH)(TiO)_i vs. SnTi—1 and Al(Nb,Ta)Ti—1 is constrained chiefly by crystal structure rather than by the composition of parent medium alone. Textural relations suggest that the Nb-moderate titanite in the core zone and entire outer zone are products of fluids-induced dissolution-reprecipitation processes. The studied niobian titanite represents a new F-enriched type from a medium-grade, calc-silicate rock.

Alunogen and meta-alunogen are the dominant phases present in transient sulphate efflorescences that are the latest products of the alteration of ignimbrite country rocks in the long-lived Te Kopia geothermal field. Meta-alunogen pseudomorphs alunogen and both species occur as white, fibrous, tangled masses, as prismatic, parallel growths, and as thin, platy, crystals, 8–15 μm across, that coalesce in an open cellular network. Small (<2 mm diam.) spherical aggregates of radiating, acicular halotrichite (Fe0.51Mg0.49Al2(SO4)4.22H2O), potash alum, mirabilite, melanterite and tschermigite are present locally. The cations needed to form these minerals derive from the host rocks with the exception of sulphur and ammonia that come from H2S and NH3 gases ascending with steam. The particular efflorescence assemblage reflects the prevailing conditions and ionic activities of a local micro-environment. Kaolinite formed by acid sulphate alteration is now being altered by steam to yield alunogen. In turn, alunogen can react with silica, or co-dissociate with silicic acid, to form kaolinite. The alternating dissolution and reprecipitation of kaolinite and alunogen moves aluminium in and through the surficial environment at Te Kopia.

Lizardite-1T crystals from Gew-graze at the Lizard, Cornwall, of an apparent composition (Mg2.94Fe0.03Al0.03)(Si1.97Al0.03)05(OH)4, have been observed to contain 2–5% of thin interstratifications of clinochlore when investigated by analytical transmission electron microscopy (TEM). The clinochlore is usually only a few unit layers thick but has an extensive lateral dimension parallel to the lizardite layers. Analytical TEM confirms the existence of very low-Al lizardite with a planar structure interstratified with occasional thin units of clinochlore containing substantial Al. Compositionally, such clinochlore (invisible by X-ray diffraction) interstratified throughout the lizardite crystals, could account for most of the Al present. We suggest that an occasional influx of Al causes the nucleation and growth of clinochlore at the expense of lizardite. The possibility of clinochlore contributing to the measured Al content in lizardite samples highlights the need for future investigations of Al-bearing serpentines to include careful examination and interpretation using imaging and analysis by TEM.

It has crept into serpentine discussions that lizardite cannot form without the coupled substitution of Al to relieve the misfit between the sheets of octahedra and tetrahedra. The lizardite at Gew-graze is almost Al-free, forms well-crystallized planar crystals and demonstrates that Al is not an essential element for lizardite crystallization.

An ‘Al-thermometer’ was applied to agate samples of volcanic parent rocks to provide information about the temperature of agate formation. The temperatures were calculated from concentrations of [AlO4]0 centres determined by electron paramagnetic resonance (EPR) measurements. The calculations for agate bands in some cases yield temperatures of up to 655°C, which are assumed to be invalid; they are thought to be artifacts resulting from non-equilibrium crystallization processes. In contrast, the formation temperatures (60–198°C) estimated for associated quartz incrustations within the agate geodes are in good accord with those calculated from oxygen isotope data. Direct estimation of the formation temperatures of agates is problematic. The best results will be obtained by analyses of associated phanerocrystalline quartz incrustations.

Crystals of laueite, Mn2+Fe23+(PO4)2(OH)2·8H2O, from the Cornelia mine open cut, Hagendorf Süd, Bavaria, are zoned due to aluminium incorporation at the iron sites, with analysed Al2O3 contents varying up to 11 wt.%. Synchrotron X-ray data were collected on two crystals with different Al contents and the structures refined. The laueite structure contains two independent Fe3+-containing sites; M2 and M3, which alternate in 7 Å corner-connected octahedral chains. The coordination polyhedra are different for the two sites, M2O4(OH)2 and M3O2(OH)2(H2O)2 respectively. The structure refinements show that Al preferentially orders into site M3. Refined site occupancies for M2 and M3 for the two crystals are: for crystal L-1, M2 = 0.70(1) Fe + 0.30(1) Al, M3 = 0.54(1) Fe + 0.46(1) Al and for crystal L-2, M2 = 0.67(1) Fe + 0.33(1) Al, M3 = 0.48(1) Fe + 0.52(1) Al. For crystal L-2, the octahedral chains have dominant Fe in M2, alternating with dominant Al in M3 along the chain, an ordering phenomenon not previously reported for laueite-related minerals.

The effects of punch geometry and sample size on forming limit diagrams in expansion areinvestigated in the case of a 2024 aluminium alloy. Four configurations were selected:flat punch (Marciniak test) or hemispheric punch and decimetric vs. centimetric toolingdimensions. Both decimetric and centimetric deep-drawing devices are associated with animage correlation tool that allows identifying without any contact the deformation on thesurface of planar or non-planar specimens. Strains on the surface of the samples areobserved by means of a double numerisation in three dimensions of the sample before andafter deformation by using stereoscopic vision and triangulation. Finally, deep-drawinglimit of the four configurations are compared in expansion state and with literature.Results mainly show that hemispherical punch allows measuring higher strains and is lesssensitive to size effect than Marciniak test.

Aluminium is the most common metallic element, but has no known biological role. It accumulates in the body when protective gastrointestinal mechanisms are bypassed, renal function is impaired, or exposure is high – all of which apply frequently to preterm infants. Recognised clinical manifestations of aluminium toxicity include dementia, anaemia and bone disease. Parenteral nutrition (PN) solutions are liable to contamination with aluminium, particularly from acidic solutions in glass vials, notably calcium gluconate. When fed parenterally, infants retain >75% of the aluminium, with high serum, urine and tissue levels. Later health effects of neonatal intravenous aluminium exposure were investigated in a randomised trial comparing standard PN solutions with solutions specially sourced for low aluminium content. Preterm infants exposed for >10 d to standard solutions had impaired neurologic development at 18 months. At 13–15 years, subjects randomised to standard PN had lower lumbar spine bone mass; and, in non-randomised analyses, those with neonatal aluminium intake above the median had lower hip bone mass. Given the sizeable number of infants undergoing intensive care and still exposed to aluminium via PN, these findings have contemporary relevance. Until recently, little progress had been made on reducing aluminium exposure, and meeting Food and Drug Administration recommendations (<5 μg/kg per d) has been impossible in patients <50 kg using available products. Recent advice from the UK Medicines and Healthcare regulatory Authority that calcium gluconate in small volume glass containers should not be used for repeated treatment in children <18 years, including preparation of PN, is an important step towards addressing this problem.

Previous papers in this series noted a positive association between aluminum water concentrations and a measure of mental impairment, and a negative association between fluoride concentrations and the same measure of mental impairment. The results obtained were qualitatively similar to the corresponding associations obtained from death certificate data that list Alzheimer's disease as the underlying cause of death. In addition, the results were also qualitatively similar to the results obtained in a number of other studies carried out at different times, in different areas and using different outcome measures for the measure of mental impairment. The present study concerns the role of iron concentrations and specifically, whether when taking iron concentrations into account, the previously noted associations involving aluminum are maintained. The results show that this seems to be the case and also suggest that iron can compete with aluminum, and can both increase or decrease the likelihood of showing signs of mental impairment. The results do not indicate consistently that by modifying the methods of water purification, using iron instead of aluminum, the treated water will be less biotoxic, although there could be instances, particularly when the aluminum concentrations are relatively high, when the use of iron compounds is beneficial.

Previous work on the association between total aluminum (Al) concentrations and a measure of cognitive impairment is extended by considering the associations between this measure of cognitive impairment, not only with total Al, but also with turbidity and DOC both of which also contain Al. The multivariate, but not bivariate, analyses show that the odds of showing indications of mental impairment increase with turbidity but decrease with DOC, and this effect is most pronounced at a medium pH. It is suggested that the two variables considered could account for some of the unexplained features of the association between Al concentrations and measures of cognitive impairment. The other associations, namely those with F, pH, source of drinking water (ground or surface) remain similar to those reported previously in this series of papers.

Following previous studies on the associations between aluminium (Al) water concentrations and relatively high risks of a measure of mental impairment, the role of silica (SiO2) as a possible confounding variable is investigated. The bivariate associations show that the lowest odds, representing an approximation of relative risks, are observed at “mild” SiO2 concentrations. Multivariate analyses indicate that, if interaction terms are included, the odds comparing higher and lower SiO2 concentrations are different than if an interaction term is not included. There are also indications that at relatively high Al levels, high SiO2 concentrations lower the odds, consistent with previous suggestions by Birchall. The implication is that when investigating the role of Al in the etiology of various measures of mental impairment, it is important to consider the effects of other water constituents, and also the different chemical forms of Al present in treated water. The desirability of additional work is stressed, preferably using more definitive outcomes than indications of mental impairment.

Using data from the Ontario Longitudinal Study of Aging (LSA) and data for aluminum and fluoride water concentration in areas where the LSA subjects resided, a preliminary analysis suggests that persons who show no indications of impaired mental functioning are more likely to have resided in areas where the aluminum concentrations (in drinking water) are relatively low and where fluoride concentrations (in drinking water) are relatively high. The difficulties in analyses of this type include the likelihood that many persons who are affected by impaired mental functioning do not respond to surveys, the identification of impaired mental functioning, and obtaining good exposure estimates of fluoride and aluminum drinking water concentrations.