The equation of state of Fo90 hydrous ringwoodite has been measured using X-ray powder diffraction to 45 GPa at the GSECARS beam line at the Advanced Photon Source synchrotron at Argonne National Laboratory. The sample was synthesized at 1400°C and 20 GPa in the 5000 ton multi anvil press at Bayerisches Geoinstitut in Bayreuth. The sample has the formula Mg1.70Fe0.192+ Fe0.023+H0.13- Si1.00O4 as determined by electron microprobe, Fourier transform infrared and Mössbauer spectroscopies, and contains ~0.79% H2O by weight. Compression of the sample had been been measured previously to 11 GPa by single crystal X-ray diffraction. A third-order Birch-Murnaghan equation of state fit to all of the data gives V0 = 530.49±0.07 Å3, K0 = 174.6±2.7 GPa and K' = 6.2±0.6. The effect of 1% H incorporation in the structure on the bulk modulus is large and roughly equivalent to an increase in the temperature of ∼600°C at low pressure. The large value of K' indicates significant stiffening of the sample with pressure so that the effect of hydration decreases with pressure.

We report preliminary petrographic and mineral chemical data for a rock hosting an unusual mineral assemblage from Långban, Värmland, Sweden. The rock is a two feldspar-scapolite-spessartine-romeite skarn. The bulk composition and high degree of enrichment in Pb, Sb and As suggest that the rock was formed by reaction between a pre-existing Mn skarn containing the chalcophiles and a potassic granite, with loss of silica, alkalis and CO2. The alkali feldspar is a Pb-rich hyalophane, averaging Or63Ab19Cs15Pb03, the plagioclase feldspar a Pb-rich labradorite, An48Ab48Or02Pb02, and the scapolite a 'mizzonite' (Ca/(Na+Ca) = 0.66—0.70). These minerals show their highest Pb contents recorded in nature to date: up to a maximum of 5.7 wt.% PbO in the hyalophane, 2.1% PbO in the plagioclase, and 5.3% PbO in the scapolite. Laser ablation ICP-MS of a scapolite grain detected substantial Be up to 1.7 wt.% BeO (0.6 Be per 12 tetrahedral cations), as well as Pb up to 7.05 wt.% PbO. The Be is incorporated into scapolite via the coupled exchange [Be(OH)][Al(CO3,SO4)]—1. This is the first documentation of scapolite as the major repository for Be in a rock.

The romeite also contains substantial Pb, and shows extensive solid solution towards end-members containing Fe3+, Ti and Sb3+. In some analyses, the dominant end-members are and its Pb analogue rather than (Ca,Pb)2Sb2O7. Complex exsolution textures are displayed in the hyalophane, by hancockite-epidote, romeite-bindheimite and hedyphane-johnbaumite. Ca-rich scapolite and hancockite appear to be new minerals for the Långban deposit.

The mineralogy appears consistent with the regional peak conditions of P = 3 kbar, T > 600°C. Several potential thermobarometers for Mn-rich skarns are identified in this rock.

Ikaite (CaCO3.6H2O), which forms in cold carbonate-rich marine environments, also crystallizes from calcite under aqueous conditions above ∼0.5 GPa at room temperature. Using synchrotron X-ray powder diffraction, measurements have been made of pressure-induced changes in unit-cell dimensions of ikaite contained in a diamond anvil cell. Ikaite shows anisotropic compressibility along the crystallographic axes in the order a > c > b up to 4 GPa. Comparison with other phases shows the relative volume compressibility of ikaite to be greater than that of gypsum (CaSO4.2H2O), calcite and aragonite. The volume of ikaite is less than that occupied by equivalent volumes of CaCO3 (calcite/aragonite) + 6H2O at all pressures below the freezing point (H2O(l) to ice VI). The bulk modulus of ikaite has been obtained from a fit to the Vinet equation of state, giving V0 = 760.3±0.1 Å3, K0 = 21.3±1.4 GPa, and K0' = 11.7±1.7. Dissolution of CaCO3 in H2O (l) at high pressure resulting in crystallization of CaCO3.6H2O suggests equilibrium behaviour between a carbonate-rich fluid species and the condensed hydrated calcium carbonate. The potential for ikaite as a candidate phase for water transport in cold subduction zones is considered.

Europium LIII-edge X-ray absorption near-edge structure (XANES) was employed to determine the Eu(II)/Eu(III) ratios in minerals. This ratio can be determined based on the peak-area ratio of white lines, the resonance peak, in normalized XANES spectra for Eu(II) and Eu(III) species. For precise determination of the Eu(II)/Eu(III) ratios, however, it was revealed that the transition probabilities for each individual Eu(II) and Eu(III) species in the system must be quantified, because we found that the peak area in normalized XANES spectra is different in each Eu(II) and Eu(III) species. Despite this ambiguity, the method was applied to Eu in natural hydrothermal apatites (Eu = 39 and 64 ppm) and fluocerite (Eu = 282 ppm). The relationship between the Eu(II)/Eu(III) ratio in these hydrothermal minerals, and the distribution coefficients of Eu(II) and Eu(III) were discussed, taking into account Eu anomalies in their REE patterns. It is considered that by combining the Eu(II)/Eu(III) ratios determined by XANES and the degree of Eu anomaly in REE patterns, we can provide new information on the distribution of Eu(II) and Eu(III) in various geochemical studies.

Biominerals are a subset of the mineral kingdom, those created by living creatures. In spite of usually fine grain size and intimate association with organic materials, biominerals are readily identified as common mineral species. Iron hydroxides and oxyhydroxides, calcium carbonates and calcium phosphates from uni- and multi-cellular species are presented as examples of biominerals, and biomineralization processes. Their special morphological, and crystal chemical, characteristics provide unique structural contributions to the life forms that create them. Investigations of novel habitats should present opportunities to expand the number of biominerals and their potential for industrial applications.

SHRIMP U-Pb zircon and titanite dating have been used to constrain the timing of mid- to lower- crustal metamorphism (∼650—700°C and 8—11 kbar) and syn-kinematic melting in the granitoid gneiss- dominated terrane south of the Barberton greenstone belt, South Africa. This study is concentrated on a clastic metasedimentary unit exposed in one of several greenstone remnants and a late-kinematic trondhjemite intrusive into spatially associated mixed gneisses. Locally, the clastic metasediments show extensive replacement of garnet and plagioclase by epidote and titanite. The titanites yield an upper intercept date of 3229±9 Ma, and provide a minimum age for the peak of metamorphism. Zircons separated from the same unit record a range of concordant and near-concordant 207Pb/206Pb dates between ∼3560 and 3230 Ma, the youngest group yielding a weighted mean date of 3227±7 Ma. This range of dates is interpreted to be due to a combination of metamorphic recrystallization and high- temperature Pb-loss in originally detrital zircons during regional metamorphism. A minimum age for the timing of deformation is given by the emplacement age of 3229±5 Ma for the late-kinematic trondhjemite. Thus, geochronological data support the notion of a major metamorphic episode that coincided with the proposed short-lived terrane accretion event in the centre of the Barberton greenstone belt.

The compositional zonation of both undeformed and plastically deformed tourmaline crystals from an amphibolite-facies mylonitic pegmatite from the Sierras Pampeanas (NW Argentina) has been investigated using electron microprobe analysis (EMPA). Undeformed tourmaline shows optical and compositional major and minor element growth zonation with a Ca- and Mg-rich rim zone and an Fe- rich core zone. The tourmaline population of the mylonite consists of crystals which appear undeformed at microscopic scale, and of weakly, moderately, and strongly deformed crystals. Depending on the intensity of plastic deformation, the optical zonation is blurred or absent, and the compositional zonation is less pronounced or destroyed. Plastic deformation mobilizes small cations (Fe2+, Mg2+) more efficiently and at lower deformation intensity than larger cations (Na+, Ca2+). In addition to intra-crystal homogenization, plastic deformation caused variable but generally minor Fe, Mg, Si, Al, Ca, and Na exchange between deformed tourmaline domains and co-existing fluid or solid phases. Dislocation creep is interpreted as the dominant deformation mechanism leading to the homogenization of the initial tourmaline growth zonation. The composition and the degree of homogeneity of deformed tourmaline domains depend on the initial composition of the growth zones, their initial volume ratio, the intensity and homogeneity of plastic deformation, and the size of the mobilized cation. Consequently, the composition of and the element distribution within plastically deformed crystals is not entirely controlled by intensive variables (P-T-X), and therefore not suitable for petrogenetic interpretation.

Detrital chrome-spinels are contaminant grains within heavy-mineral concentrates found in the Murray Basin of southeastern Australia. The presence of even minor levels of chromia in the predominantly ilmenite-rich concentrates downgrades their market value as potential feedstocks for the production of titania pigment.

Compositions from a database of close to 5000 chrome-spinel analyses show a broad range in chemistry. The major element components and their ranges (wt.%) are Cr: 3.10–52.06, Al: 0.46–32.50, Fe: 3.50–44.48 and Mg: 0.03–15.79. Minor components include; Ti: 0.01–6.41, Zn: 0.00–23.00 and Mn: 0.00–5.82. The broad variation in composition suggests multiple source areas for the chrome-spinels although detailed textural examination indicates that variation has also been introduced through pre- and post-deposition alteration processes.

The Murray Basin chrome-spinel database has the potential to be used in interpreting and predicting the effects of various processing conditions used to separate the chrome-spinels from the ilmenite.

Single crystals of Mg2GeO4 spinel, a stable analogue to mantle ringwoodite at atmospheric pressure up to 800°C, were synthesized from Mg2GeO4 olivine in hydrous conditions at 1.9 GPa and ∼1000°C. Infrared (IR) spectra show OH-stretching peaks at 3531 and 3502 cm–1. Quantification of IR spectra reveals hydrogen in the order of 5 to 10 ppm wt. H2O. A complete hydrogen/deuterium exchange was achieved at 700°C leading to a diffusion coefficient of deuterium of ∼3x10–14 m2/s. This value is of the same order as diffusion coefficients observed in other mantle minerals, such as garnet and diopside.

The O–O distance of ∽ 2.9 Å calculated from the spectra of Mg2GeO4 spinel is consistent with the GeO4 tetrahedra edge length known from crystal-structure data. Whereas the hydration mechanism and the site occupancies involved are still in discussion for mantle spinel, the IR measurements on Mg2GeO4 confirm the idea of protonation at the tetrahedral edges.

Ortho- and clinopyroxenes within partially-hydrated harzburgites from Elba and Val di Cecina (Italy) show lamellar exsolution textures and variable replacement by biopyriboles, talc-chlorite-serpentine mixed layers and serpentine. Chemical and geothermometric data suggest that the pyroxenes crystallized at 1240–1051°C, followed by subsolidus exsolution at slightly lower T (1145–1025°C for clinopyroxene lamellae + orthopyroxene matrix pairs and a 1033–982°C range for orthopyroxene lamellae + clinopyroxene matrix pairs).

Investigation by transmission electron microscopy of exsolved enstatite and augite reveals a multistage hydration process. The first stage (highest T, probably in the amphibole stability field) leads to the formation of biopyribole lamellae within exsolved augite, leaving the enstatite matrix unaffected. The second stage (~500–300°C) corresponds to the topotactic replacement of enstatite by layer silicates (talc + chlorite + serpentine, with (001)layer silicates parallel to (100)enstatite). Enstatite is also replaced by randomly oriented, poorly crystalline serpentine. The last hydration stage (<300°C) corresponds to the disappearence of augite and recrystallization of serpentine, leading to completely hydrated bastites with random lizardite lamellae, polygonal serpentine and minor chrysotile.

The mineral in bones and teeth is an impure form of hydroxylapatite (HAP), the principal impurity being 2—5 wt.% carbonate. This mineral dissolves during remodelling of bone and also in dental caries as a result of the action of acids produced by osteoclasts and by bacteria, respectively. In enamel, demineralization proceeds with preferential loss of carbonate relative to phosphate. Surprisingly, in the early stages, the demineralization is subsurface. In order to facilitate the understanding of physical chemical aspects of these processes, we have undertaken studies of demineralization in model systems. We give three examples here. The first two used scanning microradiography in which the specimen is stepped across a 10—30 μm diameter X-ray beam. Intensity measurements allow calculation of the mineral mass per unit area in the X-ray path through the specimen. In the first experiment, porous HAP sections were separated from a reservoir of acidic buffer by a column initially filled with water (the diffusion length) and scanned with the X-ray beam perpendicular to the axis of the diffusion length. The rate of total loss of mineral along each profile was calculated from the scans. The rate of demineralization fell as the diffusion length increased. We believe the explanation is that the rate-controlling step is the diffusion of dissolved HAP away from the solid to the buffer reservoir. In the second experiment, demineralizing solution and water were pumped alternately, for equal lengths of time, past blocks of porous HAP or enamel. The X-ray beam was perpendicular to the exposed surface. As the rate of switching between solutions decreased, the mean rate of demineralization also fell. We propose that this effect is due to retention of acid in the pores of the HAP during the time when water flows, allowing further demineralization to take place during this time. The third study used X-ray microtomography, a form of 3D microscopy, to study the loss of mineral in compacted carbonate apatite powders. The powders were packed in six 10 mm internal diameter acrylic cylinders to a depth of 4 mm (after pressing). One end was covered with a porous polyethylene disc and each tube placed in acidic buffer for 70 days. Periodic examination by microtomography showed the development of subsurface demineralization. Infrared spectroscopy of the dissected-out surface layers showed preferential loss of carbonate over phosphate by comparison with deeper layers. Rietveld analysis of X-ray powder diffraction data showed changes in the crystallographic structures of the apatites between the initial and dissected-out apatite.

The first Italian occurrence of cumengéite, a rare Pb and Cu hydroxychloride, is described from Vesuvius (Italy). Italian cumengéite has a volcanic origin (it occurs in the fumarole), which is unique for that mineral. The mineralogy of Vesuvius' fumarole is outlined briefly. A powder X-ray diffraction (XRD) pattern of cumengéite is presented. The crystal structure of cumengéite has been refined (R = 0.036) using single-crystal XRD data. Cumengéite is tetragonal, space group I4/mmm, a 15.1007(2), c 24.4940(4) Å. In the structure of cumengéite there are five independent Pb atoms, which are linked to 6—9 anions in five different ways. The structural study revealed the presence of two independent and previously unobserved water molecules, and led to the revision of the accepted chemical formula for the mineral: the new formula is Cu20Pb21Cl42(OH)40·6H2O. Analytical data taken from the literature for cumengéite from Boléo, Mexico (the type locality), as well as a new structural study carried out on the type material confirmed the new formula.

We have found >10 in situ microdiamonds in thin sections of eclogites from the Dabie and Su-Lu regions of central eastern China since the first occurrence of microdiamond in eclogites from the Dabie Mountains (DMT) reported in 1992. The microdiamonds are found not only in the central part but also in the northern part of the DMT. Several free crystals have been recovered from the crushed eclogites from the central DMT. Most in situ microdiamonds are inclusions in garnets but a few larger ones are intergranular. Most of the diamondiferous eclogites in the central part of the DMT are associated with coesite. Most importantly, the observation of microdiamonds in northern Dabie lead us to question the supposition that this is a low-P metamorphic terrane. All the diamondiferous eclogites from both the north and central DMT are of continental affinity as demonstrated by their negative εNd values. Therefore, both the north and central eclogite belts in the DMT are considered to be from the deep subducted terrane. Five in situ microdiamonds and two free crystals are first reported in this paper. The dimensions of the in situ microdiamonds are 30–180 µm and the free crystals are up to 400–700 mm across. All the microdiamonds are confirmed as such by Raman spectroscopy. The results of an infrared spectroscopic investigation on two larger free crystals and two in situ microdiamonds show that all the microdiamonds from both the Dabie and Su-Lu regions are mixed types IaA and IaB diamonds and there is no indication of any synthetic microdiamonds in our samples because such synthetic microdiamonds are always rich in type Ib.

The solubility and incorporation mechanisms of H and various trivalent and divalent cations in synthetic rutile have been investigated. Experiments performed using different bulk Fe2O3 contents demonstrate that Fe3+ substitutes onto the main Ti site, charge-balanced by oxygen vacancies. Under more reducing conditions in Fe-poor systems, the concentration of Ti interstitials in rutile is increased, resulting in a decrease in H solubility. Variation in the solubility of different oxides in rutile as a function of ionic radius implies substitution onto the main Ti site, probably charge-balanced by oxygen vacancies. To a lesser degree, substitution of trivalent and divalent cations is locally charge-balanced by H incorporation. Variation in OH-stretching frequencies in infrared spectra as a function of composition implies that octahedral defects and structurally-incorporated H are coupled. However, in all samples, some of the H is also decoupled from substitutional impurities, as is evident from an OH-absorption band at 3279 cm–1. This band corresponds to the main OH band seen in spectra of many natural rutiles, implying that in most rutiles, H defects are decoupled from substitutional defects.

The thermal expansion coefficients for natural troilite, FeS, Ni-rich pyrrhotite, Fe0.84Ni0.11S, and Ni-poor pyrrhotite, Fe0.87Ni0.02S, were measured during cooling by in situ neutron powder diffraction over the temperature range 873–373 K. Between 873 and 573 K, the mean thermal expansion coefficients for the three compositions are 7.4(3)×10−5 {FeS}, 8.0(4)×10−5 {Fe0.84Ni0.11S} and 8.5(4)×10−5 K−1 {Fe0.87Ni0.02S}. Below 573 down to 373 K, the first two increase considerably to 14.1(7)×10−5 {FeS} and 9.3(5)×10−5 {Fe0.84Ni0.11S} while the latter sample shows no significant variation, 8.4(5)×10−5 K−1. Below 573 K, the thermal expansion is highly anisotropic, with Δa/100 K−1 ranging from 0.89(9)% {FeS} to 0.48(12)% {Fe0.87Ni0.02S} while Δc/100 K−1 ranges from −0.39(11)% {FeS} to −0.13(2)% {Fe0.87Ni0.02S}.

Upon cooling through 573 K, troilite and pyrrhotite undergo a transition where the FeS6 octahedra distort and in the case of pyrrhotite, cation-vacancy clustering occurs. The thermal expansion coefficients are bigger for low cation-vacancy concentrations and decrease as the pyrrhotites become less stoichiometric. This indicates that the thermal expansion in these minerals is damped by vacancy ordering or clustering. The thermal expansion coefficients for troilite and pyrrhotite are amongst the largest reported for sulphide minerals and their role in the formation of ore textures is discussed briefly.

In this reconnaissance study, skeletal materials from people, dating from ∼1500 B.P., who lived by or worked at the ancient copper mines and furnaces of the Wadi Faynan in southern Jordan, were analysed using atomic absorption spectrophotometry (AAS) to determine the intensities of accumulation of copper and lead in their bones. Many of the bones analysed contained concentrations of these metals which are comparable to those of modern individuals who are heavily exposed to metals through contemporary industrial processes.

Patterns of partitioning throughout the skeleton of a number of individuals were also studied. These AAS data suggest that within the human organism there may be some ability to influence the patterns of accumulation of copper within the skeleton. The humerus was frequently found to contain more copper than other bones studied. Within the humerus itself, the medial epicondyle frequently contained the highest concentrations, which may indicate a significant degree of organization or control of the process. These metal concentration data together with their toxicological consequences suggest that the health of the ancient human populations must have been adversely affected by exposure during life to copper in the environment. They also point to the need for further detailed studies of metal partitioning within the bones of the human skeleton.

Aspidolite, the Na analogue of phlogopite, ideally NaMg3AlSi3O10(OH)2, occurring in hornfels from a contact aureole in Kasuga-mura, central Japan, has been approved as a mica species by the Commission on New Minerals and Mineral Names of the International Mineralogical Association. Aspidolite is interleaved with and surrounded by phlogopite. Based on its mode of occurrence, phlogopite is classified into two types; (1) phlogopite interleaved with aspidolite (= interleaved phlogopite) and (2) phlogopite rim. The aspidolite-phlogopite assemblage is associated with amphibole (pargasite-magnesiosadanagaite), titanite, calcite, scapolite, apatite, pyrrhotite and chalcopyrite. A representative chemical formula of aspidolite is (Na0.90K0.10)∑1.00(Mg2.27Al0.41Fe0.232+Ti0.05)∑2.96 (Al1.44Si2.56)∑4.00O10(OH1.97F0.03)∑2.00. Aspidolite has almost fully occupied the interlayer site; its Na/(Na+K) ratio ranges from 0.67 to 0.95. It has more tetrahedral Al (1.38—1.48 a.p.f.u. for O = 11) than the ideal aspidolite end-member showing progression of tschermakite-type substitution. The alternation of aspidolite and phlogopite parallel to the (001) plane may indicate a miscibility gap between these two phases. The phlogopite rim is interpreted as a later product, probably formed metasomatically. Aspidolite is optically biaxial negative with elongation positive and Z ‖ cleavage. Two polytypes (1M and 1A) of aspidolite were identified in X-ray powder diffraction patterns. Aspidolite-1M is monoclinic, space group C2/m, with refined unit-cell parameters a = 5.291(8), b = 9.16(2), c = 10.12(2) Å, β = 105.1(1)°, V = 473(1) Å3, Z = 2. Aspidolite-1A is triclinic, space group C, with a = 5.289(6), b = 9.16(1), c = 9.892(9) Å, α = 94.45(9), β = 97.74(9), γ = 90.0(1)°, V = 473.4(9) Å3, Z = 2.

Contrasting distribution patterns of Fe and Ca have been found by electron microprobe analysis (EMPA) mapping of alkali feldspar in a quartz syenite from the Patagonian Andes, Chile. They comprise mainly mantle zoning (Fe-rich, Ca-poor rims and Fe-poor, Ca-rich interiors) and corresponding patchy zoning in grain interiors. The rims are dominantly of turbid, patch microperthites associated with abundant micropores, but there remain clear, optically featureless regions almost free of micropores. The interiors are intricate mixtures of optically clear, featureless regions, and turbid, patch microperthite regions. The clear, featureless regions (Or31 –47) are of remaining exsolution lamellar cryptoperthites. The zoning patterns of Fe and Ca formed by large-scale transport over the feldspar grain during the high-temperature fluid stage. They have been modified by successive transport of Fe and Ca during the later hydrothermal development of patch microperthites and finally by K-feldspathization and albitization. Cathodoluminescence images correspond to the spatial distribution patterns of Fe overprinted by these multi-stage reactions. The original composition of the alkali feldspar before the subsolidus reactions is estimated to have been ~Or34Ab65An1, and the present bulk composition after the reactions is Or40Ab59An0.5.