Analytical transmission electron microscopy (ATEM) and X-ray absorption spectroscopy (XAS) have been used to determine the mineralogy of Pb-P deposits in the roots of the heavy metal tolerant grass cultivar Agrostis capillaris L. cv. Parys Mountain. The deposits have a pyromorphite (Pb5(PO4)3Cl)-type structure and composition although some of the Cl may be substituted by OH. Energy-dispersive mapping under the scanning electron microscope demonstrated that the majority of these deposits are present in the outer cell wall of the epidermis (the outermost layer of root cells). The phosphate composition of these grains contrasts with the phytate (C6H18O24P612−) composition of Zn-P deposits observed in similar electron microscopy studies. The physiological role of heavy metal P deposits is unclear. Heavy metal P precipitates may form actively as a tolerance mechanism to heavy metals or passively, sequestering P in a metabolically inactive form.

The mineral component (at least 95 wt. %) of dental enamel is hydroxyapatite (hydroxylapatite) with multiple substitutions. The biogenic origin of enamel is reflected in the unusual ribbon-like morphology of the crystals, which are extremely elongated in the c-axis direction, and their organized arrangement within the tissue. The study of enamel dissolution has been driven by the very high prevalence of dental caries. In enamel caries, the initial demineralization results in subsurface dissolution of mineral. While the surface remains intact, reversal of the lesion by remineralization is possible. Problems of understanding the physico-chemical processes in enamel demineralization include the general problems concerning the structure and chemistry of apatites formed in aqueous media. Added to these are the general problem of dissolution in an inhomogeneous porous medium and the complication that enamel apatite has a naturally variable composition which changes during demineralization. The use of model systems in caries research is illustrated by reference to X-ray absorption studies of enamel and synthetic analogues.

Bones from level G in the Arago cave (Tautavel, Southern France, 450 ky) were analysed using a combination of particle induced X-ray and gamma-ray emission (PIXE and PIGME) and X-ray diffraction (XRD). Human occupation and guano production by bats introduced a large amount of phosphate into the cave and as a result a decarbonated pocket was formed in the sediment, characterized by the dissolution of clay minerals, calcite and bones, and by the precipitation of phosphate secondary minerals. The Al released by clay minerals was reprecipitated as crandallite in the few remaining bones, and as montgomeryite with traces of crandallite in the surrounding sediments. Bones within the pocket have very high levels of Al, Fe, F and Zn and often have ‘diffusive’ type U-shaped concentration profiles. These profiles show that post-mortem uptake of trace elements occurred, and thus that trace element composition has to be used with care in palaeonutritional studies but is indicative of local palaeoenvironment. This uptake is complicated by a large increase in hydroxylapatite crystallinity in Palaeolithic bones compared to modern or more recent ones, as a result of the large P influx which occurred in the Arago cave after the sediment deposition.

Monazite-(Ce) from a dolomite carbonatite at Kangankunde, Malawi, is sector-zoned with variation in La2O3 of up to 6.0 wt.% and in Nd2O3 of up to 3.9 wt.% between sectors. Single crystal X-ray diffraction, backscattered electron imaging and microprobe analysis have been used to establish the relationship between the morphology and sector chemistry of this low-Th monazite, (Ce,La,Nd)PO4. Uptake of La by {011} sector surfaces is enhanced relative to that of and {100} sectors; Ce shows no partitioning differences; and uptake of Nd is more easily facilitated on and {100} surfaces relative to {011}. There appears to be a distinct relationship between the size of the REE ion and the probability of uptake via the different growth surfaces. Interpretation of this uptake behaviour, based on theories involving ‘protosites’, involves an investigation of the possible kink site geometries at edge-steps during growth. Part-formed kink sites with small entrance sizes are calculated to occur with higher frequency on relative to {011}, and this correlates with an increase in the smaller-sized REE (Nd) uptake by growth surfaces. The overall morphology and sector growth is suggested to be a function of uptake chemistry.

Secondary ion mass spectrometry (SIMS) techniques have been used to study the variation of C isotope ratio and N abundance within selected diamonds in relation to their crystal growth zones. The growth zones are seen in cathodoluminescence (CL), and include both octahedral and cuboid zones within typical diamonds of external octahedral morphology. Compositions were determined by use of a primary 133Cs+ ion beam and measurement of 12C−, 13C, and 12C14N− secondary ions at high mass resolution on a Cameca ims-4f ion microprobe at Edinburgh University.

In each of the diamonds, different growth zones have marked differences in N abundance, which are as great as 0–1400 ppm within one diamond. Changes of several hundred ppm N are common across both octahedral and cuboid growth zones, and appear sharp and abrupt at the boundaries of the growth zones. In general for the common blue CL, luminescence increases with N abundance. The changes in N abundance across fine scale (∼100 µm) growth zones show that the total N contents determined by IR spectroscopy may show great variations of abundance. In contrast, within detection limits, δ13C appears constant across many growth zone boundaries. Thus the factors controlling uptake of N from the fluid/melt reservoir in which natural diamonds grow often do not influence δ13C. No evidence of progressive variation or fractionation of C isotopes during growth was found.

Some original variation in C isotope composition may have been eliminated by diffusion of C atoms subsequent to growth, because of the storage of natural diamonds over millions of years in the Earth's mantle at temperatures of 950–1250°C. Such atomic mobility does not homogenize N distribution because of the proven tendency of N to form aggregates of atoms. A survey of experimental estimates of single atom (C) diffusion parameters, suggests that diffusion distances of ∼100 µm are likely at high temperatures (∼1100°C) over long time periods (∼1.0 Ga). Therefore, with refinement of the diffusion parameters and measurements, the extent of C isotope homogenization in natural diamonds, as well as N aggregation state, might provide quantitative evidence of their time-temperature history under mantle conditions.

Diamonds from George Creek, Colorado, preserve complex intergrowth textures between two major growth generations: homogeneous diamond with yellow-buff cathodoluminescence (CL); and diamond with blue-green CL and local growth zonation. Secondary-ion mass spectrometry (SIMS) has revealed large variations in N concentration and C isotope composition within these diamonds. Even within single stones, N contents and δ13C values can vary from 0 to 750 ppm and 0 to −20‰ respectively. These variations are similar to those recorded elsewhere for entire diamond suites. The CL characteristics correlate directly with N: diamond with yellow-buff CL has uniform N contents, whereas the zoned diamond has bright blue CL bands with high N (50–750 ppm) and dark blue or green CL bands with low N (0–20 ppm). These bands are too narrow (10–5 µm) for analysis by IR spectroscopy. δ13C also varies between the two growth generations in any one diamond plate, and to a lesser extent within these generations, but shows no consistent correlations with either CL or N. The George Creek stones preserve evidence of extreme temporal and/or spatial variations in both δ13C and N concentrations during the period of diamond growth, but the factors controlling N content during diamond growth did not control δ13C.

The hydroxy-sulphide yushkinite from the type deposit has been re-examined by electron probe microanalysis and reflectance measurement. The EPMA indicates minor Cu (up to 1.5 wt.%) and confirms an excess of V. Taking into account its composite structure (brucite-like hydroxide layer alternating with a berndtite-type sulphide layer) the proposed structural formula is, with the addition of minor intercalated Cu: [(Mg0.71Al0.36V0.03)Σ1.10(OH)2.18O0.02]Cu0.02 [VS2]. At the crystal scale, some crystal edges give a variable excess of Si and Al (in the 1/1 ratio), indicating a late topotactic intergrowth with a layered alumino-silicate (or a composite silicate-sulphide). New specular reflectance data are given in air and oil from 400 to 800 nm, with the polarization plane parallel or perpendicular to the elongation. The refractive index n and absorption coefficient k are given; no absorption band exists in the perpendicular position, with constant n close to 1.9, and k to 0.3. In a parallel position, a pseudo-transparency window is centred around 500–520 nm (∼2.4 eV). The main absorption band, centred around 730 nm (∼1.7 eV), corresponds probably to a transition t2g → eg related to intra-layer V-V bonding. Charge transfer from the brucite-type layer to the VS2 one, strictly controlled through H-bonding, induces a mean formal valency of V close to 3.6. Yushkinite is compared with other synthetic layered hydroxy-sulphides, as well as brucite-type intercalated compounds.

Pumpellyite has been found in doleritic basalt of a sheeted dyke complex drilled from 2072.1 m below sea floor in DSDP/ODP Hole 504B, south of the Costa Rica Rift, eastern Pacific. It occurs as fine-grained crystal aggregates accompanied by albite, chlorite and chalcopyrite, which partially replace a plagioclase phenocryst (An85–88) that is also associated with primary magnetite. Chemical compositions of the pumpellyite vary antithetically in relation to Fe* and Al as well as Fe* and Mg, indicating the dominant substitution of Fe3+ by Al with the minor substitution of Fe2+ by Mg. Such compositional variations overlap with those of prehnite-pumpellyite facies rocks dredged from other oceanic ridges and intra-oceanic arcs, and those of similar facies rocks from ophiolites, but are aluminous compared with those of zeolite facies metabasites in ophiolites. These observations suggest that the breakdown of the plagioclase phenocryst and magnetite in the presence of a Cu- and S-bearing fluid phase led to the formation of pumpellyite + albite + chlorite + chalcopyrite during oceanic ridge hydrothermal alteration.

The crystal structure of barstowite (3PbCl2·PbCO3·H2O, P21/m, a = 4.2023(5), b = 9.2020(7), c = 16.6608(6)(Å), β = 91.829(9)°) from Bounds Cliff, St Endellion, Cornwall, has been determined to an R = 0.036. The structure can be described in terms of three layers stacked along [001] in the sequence …CACBCACBC… to give a 16.7 Å repeat. Layer A consists of face-sharing PbCl8 distorted square antiprisms. Layer B is composed of Pb coordinated to 5 Cl and 2 O each with two H to form H2O groups. Layer C is formed by Pb coordinated to 5 Cl and 3 O which are from CO3 groups. The H positions are deduced and are H-bonded to O from carbonates. The structural details were in agreement with previous deductions based on infrared spectra.

Itoigawaite, SrAl2Si2O7(OH)2·H2O, is a new member of the lawsonite group found in the Itoigawa-Ohmi district, central Japan. It is orthorhombic, Cmcm, a = 6.031(2), b = 8.945(2), c = 13.219(4) Å, Z = 4. The strongest lines in the X-ray powder diffraction pattern are 4.68 (s) (111), 4.26 (vs) (021), 3.31 (vs) (113), 2.75 (vs) (114, 202), 2.68 (vvs) (130), 2.63 (s) (131), 2.50 (s) (220, 203, 132), 2.45 (s) (221). Electron microprobe analysis gave SiO2 32.98, TiO2 0.87, Al2O3 27.67, Fe2O3 0.39, MgO 0.27, CaO 0.45, SrO 27.71, H2O (diff.) 9.66, total 100.00 wt.%, corresponding to (Sr0.97Ca0.03Mg0.02)Σ1.02 (Al1.97Ti0.04Fe0.02)Σ2.03Si1.99H3.89O10 on the basis of O = 10. It is transparent, blue in colour with vitreous lustre. The streak is white and the cleavage good in one direction. The hardness is 5–5.5. The calculated density is 3.3 g cm−3. It is colourless in thin section and optically biaxial positive with α = 1.664 (2), β = 1.674 (2), γ = 1.688 (2) and 2V(calc.) = 81°. It occurs in a thin veinlet cutting a lavender-coloured Ti-bearing jadeitite. The veinlet includes irregularly-shaped aggregates composed of minute tabular crystals of itoigawaite up to 50 µm across and minute jadeite crystals with interstitial natrolite aggregates. Itoigawaite is considered to be crystallized from fluid during later stage activity of high-P/T metamorphism. The name is for the locality.

High resolution transmission electron microscopy studies on the lillianite group minerals from the Ivigtut cryolite deposit, Ivigtut, South Greenland revealed the existence of disordered intergrowths of lillianite/gustavite-like blocks (N − 4) and heyrovskyite-like (N = 7) structural blocks. One disorder sequence is examined in detail, which gave an average homologue number N = 4.92 corresponding to a composition of Pb3.922xBi2·xAgxS6.92 with x ≈ 1.2. An Axial Next-Nearest Neighour Ising model was used to follow the fluctuations in the average homologue number N across the crystal. This yielded compositional fluctuations of the order of 70–170 Å over a 1800 Å region of the crystal, with a 202 Å lamella of ordered vikingite. Trends in the randomness of the gustavite-vikingite intergrowth were evaluated and the dominant slab sequence was found to be 4,4,4,7 and 4,4,7,7, suggesting that some longer period homologues may be stable. A number of defects were noted in which changes in slab widths were accommodated. The origin of these partially ordered/disordered lillianite homologues is discussed.

Some important and interesting data on the O, C and Sr isotopic compositions of rocks associated with the Bayan Obo Fe-Nb-REE deposit have been reported by Le Bas et al. (1997). However, a number of points relating to the interpretation of these data, and also to the terminology adopted, are worthy of further discussion. The essence of this discussion is that some of the geochemical and isotopic signatures found at Bayan Obo are not exclusively consistent with an igneous origin. A replacement hypothesis involving deep-sourced fluids could also explain the pattern of data, if minor carbonatitic intrusions into a sedimentary sequence are considered.

Over the last 50 years many definitions of element substitution series have been proposed for describing natural Fe-Li micas with complex chemical compositions. In order to compare these definitions and ascertain their reliability, a new geometric frame composed of ideal mica points, mica joins (segments), substitution vectors and substitution planes is constructed to express the entire substitution system of ideal Fe-Al-Li micas. The frame is built in composition space with the coordinate system (0; Si, AlVI AlIV, Fe2+, Li, □VI, K), but has a 3-dimensional analogue, i.e. a visual image.

Using this frame, it has been proved that there are only five possible types of replacement for definitions of Fe-Li micas, and that all possible types have been suggested except the AlIV-constant. Furthermore, it has been proved that the main point in different definitions is that the replacement of Li by Fe2+ needs to be balanced with AlIV, AlVI, or □VI. In order to solve this problem, a set of formulae determining spatial relations between geometric elements in the frame is suggested. With these formulae, the abstract frame is suggested to be a datum system used to ascertain quantitatively the reliability of definition of natural Fe-Li micas.