Progressive alteration by seawater of an andesite in the Aegean Island of Milos and an ignimbrite in the Aegean Island of Kimolos, Greece, formed bentonites with or without zeolites. Both profiles are dominated by migration of alkalis and uptake of Mg, Fe and H2O, while Al and Ti are immobile. The relative removal of alkalis controls the formation of either smectite or zeolites. The behavior of Ca and Si depends on the chemistry of the parent rock. In the rhyolitic profile, alteration is controlled by gain of Mg, Fe2+ and Ca and loss of Na, K and Si, while in the andesitic profile by gain of Mg and Fe2+ and loss of Na, K and Ca. In both profiles, significant uptake of SO4- was not observed. Moreover Zr, Nb, V and Ni are immobile and have been enriched residually, while Sr, Rb and Y are lost in both profiles. Thorium is immobile in the rhyolitic profile but is leached in the andesitic profile. Also, the rare earth elements (REE) display fractionation in both profiles; the degree of fractionation increases with the degree of alteration to bentonite. Fractionation of the REE in both profiles and mobility of Th in the andesitic profile are related to the existence of monazite (rhyolitic profile) and apatite (andesite profile). The REE and Th appear to partition into phosphates rather than smectite.

The mobility of Y coupled with the immobility of Nb increases the Nb: Y ratio with advancing alteration, rendering discrimination diagrams that use this ratio to determine the nature of the protoliths misleading. Mass balance calculations showed that in the smectite-rich zones the water: rock (WR) ratio might be as high as 13:1 in both profiles, while in the zeolite-bearing zones it is about 5.5:1. Such WR ratios explain the observed extensive mass transfer and suggest that the pore fluid chemistry might overprint the chemical characteristics of the parent rocks controlling smectite and bentonite chemistry.

The crystal structure of faustite, ZnAl6(PO4)4(OH)8.4H2O, was determined using single-crystal data (Mo-Kα X-radiation, CCD area detector, 1624 unique reflections, R1 = 4.91%, wR2 = 9.23%), and compared with results of a reinvestigation of the structure of its copper analogue turquoise, CuAl6(PO4)4(OH)8.4H2O (2737 unique reflections, R1 = 2.81%, wR2 = 6.90%). Both are isostructural and crystallize in space group P, with a = 7.419(2) [turquoise: 7.410(1)], b = 7.629(3) [7.633(1)], c = 9.905(3) [9.904(1)] Å, α = 69.17(2) [68.42(1)], β = 69.88(2) [69.65(1)], γ = 64.98(2) [65.05(1)]°, V = 462.2(3) [460.27(10)] Å3, and Z = 1. The structure consists of distorted MO6 polyhedra (M = Zn, Cu), AlO6 octahedra and PO4 tetrahedra. By edge- and corner-sharing of these polyhedra a fairly dense three-dimensional framework is formed which is further strengthened by a system of hydrogen bonds. The metal atoms in the unique MO6 (M = Zn or Cu) polyhedron show a distorted [2+2+2]-coordination, the distortion being more pronounced in turquoise. About 10% of the M site is vacant in both minerals. In turquoise, a previously undetected structural site with a very low occupancy of (possibly) Cu is present at the position (Ý,0,Ý).

The crystal structure of ulrichite, CaCu2+(UO2)(PO4)2·4H2O (space group P21/c, a = 12.784(3), b = 6.996(1), c = 13.007(3)Å, β = 91.92(1)°, V = 1162.7(4)Å3, Z = 4) was redetermined using X-ray diffraction data measured from a twinned crystal with Mo-Kα radiation and a CCD area detector (2510 unique reflections with Fo > 4σ(Fo), R1 = 8.8%). Ulrichite crystallizes in space group P21/c rather than C2/m reported previously. The newly determined atomic positions give reasonable coordination polyhedra. One unique Ca atom is irregularly coordinated by eight O atoms (<Ca–O> = 2.46 Å). One unique U atom shows a {2+5} coordination with characteristic bond angles and lengths (1.806(11)Å, 1.842(12)Å and five bonds between 2.252(15) and 2.441(11)Å). Furthermore, the structure contains groups in which strongly elongated CuO6 ‘octahedra’ (also describable as CuO4 squares) are corner-linked to two PO4 tetrahedra via two opposite, equatorial O atoms. Edge- and corner-sharing UO7, CaO8 and PO4 polyhedra form heteropolyhedral sheets parallel to (001) that are linked to adjacent sheets via the CuO6 ‘octahedra’ and hydrogen bonds.

The structure hierarchy hypothesis states that structures may be ordered hierarchically according to the polymerization of coordination polyhedra of higher bond valence. A mathematical hierarchy is an ordered set of elements where the ordering reflects a natural hierarchical relation between (or arrangement of) the elements. Here, I review the structure hierarchies for the borate, uranyl oxide, phosphate, sulfate, beryllate and oxide-centred Cu, Pb and Hg minerals (plus synthetics where appropriate). Structure hierarchies have two functions: (1) they serve to organize our knowledge of minerals (crystal structures) in a coherent manner; (2) if the basis of the classification involves factors that are related to the mechanistic details of the stability and behaviour of minerals, then the physical, chemical and paragenetic characteristics of minerals should arise as natural consequences of their crystal structures and the interaction of those structures with the environment in which they occur. We may justify the structure hierarchy hypothesis by considering a hypothetical structure-building process whereby higher bond-valence polyhedra polymerize to form the structural unit. The clusters constituting the FBBs (fundamental building blocks) may polymerize to form the following types of structural unit: (1) isolated polyhedra; (2) clusters; (3) chains and ribbons; (4) sheets; and (5) frameworks. The major advantage of this approach to structure hierarchy is the fact that the hypothetical structure-building process outlined above resembles (our ideas of) crystallization from an aqueous solution, whereby complexes in aqueous and hydrothermal solutions condense to form crystal structures, or fragments of linked polyhedra in a magma condense to form a crystal. Although our knowledge of these processes is rather vague from a mechanistic perspective, the foundations of the structure hypothesis give us a framework within which to think about the processes of crystallization and dissolution.

The procedure for deriving interatomic potentials for molecular ionic materials, using empirical fitting procedures, is described. Potentials are obtained for carbonates, phosphates and perchlorates, and used to calculate crystal and lattice properties which are compared with available experimental data.

Polyminerallic, sulphidic mine wastes were treated with KH2PO4-H2O2 solutions to determine whether the formation of solid phosphate coatings inhibits sulphide oxidation and metal and metalloid mobility. The waste rocks were metal (PbZnCu) and metalloid (AsSb) rich and consisted of major quartz, dickite, illite and sulphide minerals (e.g. galena, chalcopyrite, tetrahedrite, sphalerite, pyrite, arsenopyrite) as well as minor to trace amounts of pre- and post-mining oxidation products (e.g. oxides, hydroxides, arsenates and sulphates). Scanning electron microscopy observations of the waste material treated with KH2PO4-H2O2 solutions showed that metal, metal-alkali and alkali phosphate precipitates formed and coatings developed on all sulphides (with the exception of tetrahedrite). The abundance of phosphate phases was dependant on the availability of metal and alkali cations in solution. In turn, the release of cations was dependent on the amount of sulphide oxidation induced during the experiment or the presence of soluble oxidation products. Lead and to a lesser degree Cu and Zn phosphate coatings remained stable during H2O2 leaching, preventing acid generation and metal release. In contrast, the lack of phosphate coating on tetrahedrite and arsenopyrite allowed oxidation and leaching of As and Sb to proceed and mobilized As and Sb did not form phosphate phases. As a result, As and Sb displayed the greatest release from the coated waste. Thus, the application of KH2PO4-H2O2 solutions to partly oxidized, polyminerallic mine wastes suppresses sulphide oxidation and is most effective in inhibiting Pb (Cu and Zn) release. However, the technique appears ineffective in preventing metalloid (As, Sb) leaching from tetrahedrite- and arsenopyrite-bearing wastes.

Mn-rich graftonite, (Ca,Mn2+)(Fe2+,Mn2+)2(PO4)2, ferrisicklerite, Li1–x(Fe3+,Mn2+)PO4, manganoan apatite, (Ca,Mn2+,Fe2+Mg)(PO4)3Cl, staně kite, Fe3+Mn2+O(PO4) and Mn-rich vivianite, (Fe2+)3(PO4)2·8H2O, occurring in a granitic pegmatite at Soè Valley (central Alps, Italy) were characterized by powder and single-crystal X-ray diffraction (XRD) and electron microprobe analyses. Geochemically, the Mn-rich graftonite phases are poorly evolved Fe/Mn-phosphates of rare-earth elements-lithium (REE-Li) granitic pegmatites. The assemblage Mn-rich graftonite + ferrisicklerite + staněkite has rarely beendocumen ted in pegmatites. Inthe Soè Valley pegmatite, ferrisicklerite forms exsolution lamellae with Mn-rich graftonite associated with manganoan apatite and staněkite. Graftonite is associated with Mn-rich vivianite. Powder and single-crystal XRD data indicate that the unit-cell volume of graftonite increases as a function of Mn2+ content. Staněkite shows a distinctly smaller unit-cell volume with respect to previously reported staněkites, probably due to reduced Mn2+. Vivianite with significant Mn2+ has a unit-cell volume similar to nearly Mn-free vivianite. The formation of Mn-rich graftonite and manganoan apatite is related to destabilization of Mn-rich almandine and biotite during pegmatite formation. Ferrisicklerite forms exsolution lamellae along the 010 cleavage planes of Mn-rich graftonite, whereas staněkite forms by alterationof ferrisicklerite and Mn-rich vivianite due to circulation of late-stage hydrothermal fluids.

The new mineral fluorarrojadite-(BaNa), ideally BaNa4CaFe13Al(PO4)11(PO3OH)F2 was found on the dump of Elisabeth adit near Gemerská Poloma, Slovakia. It occurs in hydrothermal quartz veins intersecting highly fractionated, topaz–zinnwaldite S-type leucogranite. Fluorarrojadite-(BaNa) is associated with fluorapatite, ‘fluordickinsonite-(BaNa)’, triplite, viitaniemiite and minor amounts of other minerals. It forms fine-grained irregular aggregates up to 4 cm x 2 cm, which consist of individual anhedral grains up to 0.01 mm in size. It has a yellowish-brown to greenish-yellow colour, very pale yellow streak and a vitreous to greasy lustre. Mohs hardness is ~4½ to 5. The fracture is irregular and the tenacity is brittle. The measured density is 3.61(2) g cm–3 and calculated density is 3.650 g cm–3. Fluorarrojadite-(BaNa) is biaxial (+) and nonpleochroic. The calculated refractive index based on empirical formula is 1.674. The empirical formula (based on 47 O and 3 (OH + F) apfu) is A1(Ba0.65K0.35)Σ1.00 A2Na0.35 B1(Na0.54Fe0.46)Σ1.00 B2Na0.54Ca(Ca0.74Sr0.20Pb0.02Ba0.04)Σ1.00Na2 Na3Na0.46 M(Fe7.16Mn5.17Li0.37Mg0.12Sc0.08Zn0.06Ga0.02Ti0.02)Σ13.00 Al1.02P11O44PO3.46(OH)0.54 W(F1.54OH0.46). Fluorarrojadite-(BaNa) is monoclinic, space group Cc, a = 16.563(1) Å, b = 10.0476(6) Å, c = 24.669(1) Å, β = 105.452(4)°, V = 3957.5(4) Å3 and Z = 4. The seven strongest reflections in the powder X-ray diffraction pattern are [dobs in Å, (I), hkl]: 3.412, (21), 116; 3.224, (37), 206; 3.040, (100), 42$\bar 4$; 2.8499, (22), 33$\bar 3$; 2.7135, (56), 226; 2.5563, (33), 028 and 424; 2.5117, (23), 040. The new mineral is named according to the nomenclature scheme of arrojadite-group minerals, approved by the IMA CNMNC. In fluorarrojadite-(BaNa), Fe2+ is a dominant cation at the M site (so the root-name is arrojadite) and two suffixes are added to the root-name according to the dominant cation of the dominant valence state at the A1 (Ba2+) and B1 sites (Na+). A prefix fluor is added to the root-name as F– is dominant over (OH)– at the W site.

Three durophagous mosasaur species are represented by isolated teeth in the Upper Cretaceous (Maastrichtian) phosphatic beds of Morocco. Globidens phosphaticus nov. sp. is characterised mainly by a strong heterodonty, with mid-posterior teeth being bulbous, irregularly oval in crosssection, and having an inflated posterior surface, a large eccentric located and recurved apical nubbin, vertical sulci on medial and lateral faces, no carinae and an enamel surface covered by anastomosing ridges. Teeth of Prognathodon currii are broad and tall, straight cones, slightly swollen at the base, and with two serrated carinae. These two taxa have been collected from all the phosphatic series (lower to upper Maastrichtian) in the Ganntour Basin (Morocco). Globidens phosphaticus nov. sp. is probably also represented at other Maastrichtian phosphatic sites along the southern margin of the Mediterranean Tethys. Prognathodon currii was previously known only from the Upper Cretaceous phosphates of Negev. Of the third taxon, Carinodens belgicus, only a single tooth (now lost) is known from the Oulad Abdoun Basin (Morocco); this is low, swollen, laterally compressed and bicarinate with a large apical nubbin. Previous records of this species include Europe and Brazil.

The systems PbO–Bi2O3–P2O5/As2O5/V2O5 have been studied with respect to their compounds and solid solutions. A number of new compounds, particularly with high-Bi contents were found. Most of them are structurally closely related to the CaF2 and δ-Bi2O3 structures. Several binary and ternary solid solutions with P/As/V substitutions were investigated.

Sediment formation was investigated during UHT treatment of goats' milk, subjected to indirect treatment at 140°C for 2 s, with upstream homogenisation. Stabilisers evaluated were sodium hexametaphosphate (SHMP), trisodium citrate (TSC), disodium hydrogen orthophosphate (DSHP), and sodium dihydrogen orthophosphate (SDHP). With no added stabiliser, goats' milk produced a heavy sediment on UHT treatment. Addition of SDHP reduced pH, had little effect on ionic calcium and did not substantially reduce sediment. However, addition of SHMP, DSHP and TSC each reduced ionic calcium, increased ethanol stability and reduced sediment. Following stabiliser additions, there was a good correlation between ethanol stability and ionic calcium (R2=0·85) but not between ethanol stability and pH (R2=0·08). Overall, reducing ionic calcium reduced the amount of sediment formed for all these three stabilisers, although there was no single trend line between sediment formation and ionic calcium concentration. Sediment formation was not well correlated with pH for TSC or for SHMP, but it was for DSHP, making it the only stabiliser where sediment formation correlated well both with ionic calcium and pH, which might account for its effectiveness at higher ionic calcium levels. Sediment was much reduced when the temperature was reduced from 140°C to 125°C and 114°C. There were no further changes in sediment on storage for two weeks. Analysis of the sediment showed that it was predominantly fat and protein, with a mass ratio ranging between 1·43:1 and 1·67:1. Its mineral content was usually less than 5% of dry weight. The maximum amounts of P and Ca were found to be 2·32% and 1·63%, respectively.