During an electron microscope study of the weathering of granite from southern New South Wales, Australia, an assemblage of minerals including florencite and rhabdophane was discovered replacing apatite. Light rare earth elements released from allanite early in weathering apparently combined with P released by leaching of primary apatite to form secondary phases exhibiting a range of morphologies and compositions. Chondrite normalized fractionation patterns La > Nd > Sm > Ce; La > Ce > Nd ≥ Sm and La = Sm = Nd > Ce were identified. The rare earth elements were present in very small crystals and aggregates of secondary minerals (< 10 μm) and coexisted with clays and secondary Fe-Ti oxides. The weathered granite was enriched about 6 to 10 times in all rare earth elements except Ce relative to fresh granite if the abundances were corrected for apparent enrichment due to reduction in density. The rare earth elements were probably derived from higher in the weathering profile, possibly by destruction of florencite and rhabdophane in very intensively weathered rock. Ce remained relatively immobile during weathering, probably due to its oxidation to Ce4+.

Oxygen isotope composition of three types of unique nodules which consist of amorphous silica-apatite, cristobalite-apatite and tridymite-apatite associations interspersed amidst basaltic pyroclastics from the Har Peres volcano, Golan Heights, Israel is reported. Unusual isotopic temperature (75°C estimated from oxygen isotope fractionation between cristobalite (δ18O = +25.5‰)-apatite (δ18O = +12.9‰) pair suggests that the nodule was not formed by present-day pedogenesis as has been previously proposed, but was a xenolith incorporated probably from the underlying siliceous phosphorites at a higher temperature. An observed negative oxygen isotopic fractionation (δ18O = −5.1‰) between tridymite (δ18O = +9.9‰) and associated apatite (δ18O = +15.0‰) is indicative of the nodular formation under disequilibrium conditions. A plausible mechanism of formation of the apatite (and calcite) associated with tridymite is an epitaxial overgrowth on template tridymite of magmatic origin under the current weathering regime. Oxygen isotopic evidence indicates a complicated origin for the nodules.

The Wulanba granite, consisting of biotite monzogranite and syenogranite, is located in the southern part of the Great Xing’an Range, NE China. Whole-rock major- and trace-element geochemistry suggests the Wulanba granite is a high-K–shoshonitic, slightly peraluminous and highly differentiated I-type granite. The Sr–Nd–Hf isotopes indicate that it originated from partial melting of juvenile crust derived from the depleted mantle with a minor input of old crust. The relatively young T2DM and tDM2 ages indicate it was most likely derived from a Late Neoproterozoic to Early Palaeozoic source. We have demonstrated that the biotite monzogranite is the ore-related intrusion of the Haobugao Zn–Fe mineralization based on the following geological, geochronological and geochemical evidence: (1) the chalcopyrite/pyrite in the biotite monzogranite and the continuous mineralization of drill core ZK2508; (2) the consistence of the emplacement age of the biotite monzogranite (~141–140/138 Ma) with the skarn mineralization age (~142 Ma); and (3) the presence of rich ore-forming elements (Fe–Zn–Cu) in the biotite monzogranite, and the similar Pb compositions of the sulfides from the Haobugao deposit and the biotite monzogranite. Compared to the barren syenogranite, the fertile biotite monzogranite is more oxidized, while the edges of the apatite grains in the biotite monzogranite are more oxidized than the centres. The average F/Cl ratio of the fertile biotite monzogranite (~123.45) is much higher than that of the barren syenogranite (~73.98). We conclude that these differences reflect unique geochemical signatures, and the geochemical composition of the apatite can be used to infer the economic potential of granites.

The Good Hope carbonatite is located adjacent to the Prairie Lake alkaline rock and carbonatite complex in northwestern Ontario. The occurrence is a heterolithic breccia consisting of diverse calcite, dolomite and ferrodolomite carbonatites containing clasts of magnesio-arfvedsonite + potassium feldspar, phlogopite + potassium feldspar together with pyrochlore-bearing apatitite clasts. The apatitite occurs as angular, boudinaged and schlieren clasts up to 5 cm in maximum dimensions. In these pyrochlore occurs principally as euhedral single crystals (0.1–1.5 cm) and can comprise up to 25 vol.% of the clasts. Individual clasts contain compositionally- and texturally-distinct suites of pyrochlore. The pyrochlores are hosted by small prismatic crystals of apatite (~100–500 μm × 10–25 μm) that are commonly flow-aligned and in some instances occur as folds. Allotriogranular cumulate textures are not evident in the apatitites. The fluorapatite does not exhibit compositional zonation under back-scattered electron spectroscopy, although ultraviolet and cathodoluminescence imagery shows distinct cores with thin (<50 μm) overgrowths. Apatite lacks fluid or solid inclusions of other minerals. The apatite is rich in Sr (7030–13,000 ppm) and rare earth elements and exhibits depletions in La, Ce, Pr and Nd (La/NdCN ratios (0.73–1.14) relative to apatite in cumulate apatitites (La/NdCN > 1.5) in the adjacent Prairie Lake complex. The pyrochlore are primarily Na–Ca pyrochlore of relatively uniform composition and minor Sr contents (<2 wt.% SrO). Irregular resorbed cores of some pyrochlores are A-site deficient (>50%) and enriched in Sr (6–10 wt.% SrO), BaO (0.5–3.5 wt.%), Ta2O5 (1–2 wt.%) and UO2 (0.5–2 wt.%). Many of the pyrochlores exhibit oscillatory zoning. Experimental data on the phase relationships of haplocarbonatite melts predicts the formation of apatite and pyrochlore as the initial liquidus phases in such systems. However, the texture of the clasts indicates that pyrochlore and apatite did not crystallise together and it is concluded that pyrochlores formed in one magma have been mechanically mixed with a different apatite-rich magma. Segregation of the apatite–pyrochlore assemblage followed by lithification resulted in the apatitites, which were disrupted and fragmented by subsequent batches of diverse carbonatites. The genesis of the pyrochlore apatitites is considered to be a process of magma mixing and not simple in situ crystallisation.

Fluorapatite with monazite-(Ce) and xenotime-(Y) microinclusions occurs in the lithium–caesium–tantalum pegmatite body A of the Volta Grande mine, Minas Gerais state, Southeast Brazil. The fluorapatite displays faint zoning, detected mainly by cathodoluminescence. Electron probe and laser ablation analyses indicate that zoning in the fluorapatite corresponds to variation in Mn and rare-earth element (REE) content. Such compositional variation is attributed to partial removal of the REE from the fluorapatite structure during a dissolution–reprecipitation process, forming monazite-(Ce) and xenotime-(Y) microinclusions in the REE-depleted zones of the fluorapatite. These inclusions exhibit an inherited geochemical signature, manifested by low Th and U concentrations when compared to monazite and xenotime crystallised from melts. Rhodochrosite and calcite inclusions are also associated with monazite-(Ce) and xenotime-(Y) and are probably products of the same process, recycling Ca, Mn, and CO32− from the fluorapatite through the following reaction: [Ca(5–2a–b–½x),Naa,(Y + REE)a,Mnb][(PO4)3–x(CO3)x(F)] + Fluid[a(2Ca2+ + P5+) + (x–b)(Ca2+) + H2O)] → [Ca5(PO4)3(F,OH)] + a[(Y + REE)PO4] + b[Mn(CO3)] + (x–b)[Ca(CO3)] + Fluid a[Na+].

On the basis of new fluid-inclusion analyses, we propose that a hot (T > 204.5°C), salty (16 wt.% eq. NaCl, attributed to LiCl), hydrous fluid mediated the dissolution–reprecipitation of the fluorapatite. This fluid corresponds to similarly described Li-rich fluids which were suggested to have re-equilibrated the mineralogical assemblage at the Volta Grande mine.

The Stac Fada Member of the Stoer Group, within the Torridonian succession of NW Scotland, is a melt-rich, impact-related deposit that has not been conclusively correlated with any known impact structure. However, a gravity low approximately 50 km east of the preserved Stac Fada Member outcrops has recently been proposed as the associated impact site. We investigate the location of the impact structure through a provenance study of detrital zircon and apatite in five samples from the Stoer Group. Our zircon U–Pb data are dominated by Archaean grains (> 2.5 Ga), consistent with earlier interpretations that the detritus was largely derived from local Lewisian Gneiss Complex, whereas the apatite data (the first for the Stoer Group) display a single major peak at c. 1.7 Ga, consistent with regional Laxfordian metamorphism. The almost complete absence of Archaean-aged apatite is best explained by later heating of the > 2.5 Ga Lewisian basement (the likely source region) above the closure temperature of the apatite U–Pb system (c. 375–450°C). The U–Pb age distributions for zircon and apatite show no significant variation with stratigraphic height. This may be interpreted as evidence that there was no major change in provenance during the course of deposition of the Stoer Group or, if there was any significant change, the different source regions were characterized by similar apatite and zircon U–Pb age populations. Consequently, the new data do not provide independent constraints on the location of the structure associated with the Stac Fada Member impact event.

Apatite-type materials AI4AII6(BO4)6X2 have two unique cations sites AI and AII, which can host large mono-, di- tri- and tetra-valent cations. The average cation radii will affect the twist angle and lattice constants. However, there are few reports on the influence of B site substitutions on the twist angle and lattice parameters. It is believed that the lattice constant variation as a function of B site substitutions may not follow the same twist-angle model as proposed for A site. This work reports our results on the crystal chemistry of synthetic apatite Ca10(VxP1−xO4)6F2 obtained through the crystal structure characterization using Rietveld refinement and high-resolution transmission electron microscopy. The quantification of vanadium/phosphorus partitioning in BO4 tetrahedra showed that equilibrium with more than 70% substitution of phosphorous by vanadium was difficult to achieve unless longer annealing (about 1 week at 900 °C) was employed. In comparison with the apatites with different ionic radii at AI and AII sites, Ca10(VxP1−xO4)6F2 apatites with different ionic radii at B site show little twist angle variation for the whole series, which indicates that the dilation of unit cell constants is mainly because of the expansions of BO4 tetrahedra when A site cation is fixed.

A mineral, mimetite Pb5(AsO4)3Cl, is one of the most insoluble minerals and continues to be considered a viable remedial strategy for immobilization of Pb and As from contaminated soils. It has been recognized that many well-known, naturally-occurring, and synthetic chelators strongly influence dissolution processes in near-surface geological environments. In this study, crystals of mimetite were observed in scanning electron microscopy (SEM) and atomic force microscopy (AFM) before and after dissolution in EDTA (ethylene diamine tetra-acetic acid) solution. Direct in situ observations at room temperature made in an AFM fluid cell revealed that the grain surface roughness has increased due to development of etch pits. Both hexagonal and prismatic walls developed dissolution features between 0.6 and 1.2 µm, respectively, during duration of the experiment. AFM observations suggest surface-controlled dissolution dominated step retrieval on both prismatic and hexagonal surfaces. SEM observations showed the development of rounded edges on hexagonal walls and elongated, oval etch pits on the prismatic wall. These results, representing early dissolution patterns on mimetite surfaces, might suggest that low pH conditions in soils containing organic acids similar to EDTA might contribute to remobilization of Pb and As from mimetite when applied to stabilization of these toxic metals in contaminated soils.

Through a correlative analytical approach encompassing backscattered electron scanning electron microscopy (BSE-SEM), energy dispersive X-ray spectroscopy (EDX), and micro-Raman spectroscopy, the composition of the mineralized biofilm around a dental implant, retrieved due to peri-implantitis, was investigated. The mineralized biofilm contains two morphologically distinct regions: (i) bacteria-containing zones (Bact+), characterized by aggregations of unmineralized and mineralized bacteria, and intermicrobial mineralization, and (ii) bacteria-free zones (Bact−), comprised mainly of randomly oriented mineral platelets. Intramicrobial mineralization, within Bact+, appears as smooth, solid mineral deposits resembling the morphologies of dental plaque bacteria. Bact− is associated with micrometer-sized Mg-rich mineral nodules. The Ca/P ratio of Bact+ is higher than Bact−. The inorganic phase of Bact+ is carbonated apatite (CHAp), while that of Bact− is predominantly octacalcium phosphate (OCP) and whitlockite (WL) inclusions. Compared with native bone, the inorganic phase of Bact+ (i.e., CHAp) exhibits higher mineral crystallinity, lower carbonate content, and lower Ca/P, C/Ca, Mg/Ca, and Mg/P ratios. The various CaPs found within the mineralized dental biofilm (CHAp, OCP, and WL) are related to the local presence/absence of bacteria. In combination with BSE-SEM and EDX, micro-Raman spectroscopy is a valuable analytical tool for nondestructive investigation of mineralized dental biofilm composition and development.

Exsolution lamellae of baryte, Fe sulfides, Cu sulfides and Fe oxides were observed in apatite enclosed in garnet and omphacite and their intergranular spaces in ultrahigh-pressure eclogite in the Moldanubian Zone, Czech Republic. Micro-textural relations and compositional mapping of the apatite indicates a close relationship between the density of the exsolution lamellae and compositional domains that are rich in sulfur and iron. No relation between compositional domains and fluorine or chlorine content or any evidence of apatite metasomatisation was observed. On the basis of cathodoluminescence images, the compositional domains reflect sector zoning in apatite crystals by preferential uptake of elements due to differences in surface charge and morphology on the growth plane. It is concluded that the lamellae are products of exsolution in a closed system resulting from temperature decrease during metamorphism.

Phosphorus contents in cumulus rocks occurring close to the level of apatite appearance in the basic rocks of the Bushveld Complex, South Africa, provide a method of calculating the proportion of intercumulus component in these rocks. Previous experimental studies have accurately constrained the phosphorus content of magmas when apatite becomes stable. The ratio of the phosphorus content in the cumulates immediately below the appearance of apatite to this liquid composition defines the proportion of trapped liquid.

Application of this method to rocks from the uppermost mafic rocks of the Bushveld Complex leads to the conclusion that there is from 1 to 6 per cent intercumulus component. Many of these rocks are multiphase cumulates and in such rocks estimation of intercumulus component from textural criteria is difficult.

If crystals grow In situ on the floor of the magma chamber such small proportions of interstitial component can be produced without appealing to excessive diffusion and circulation of magma through an unconsolidated crystal pile. The geometry of the intrusion as well as its size might have a major influence on the proportion of the liquid ultimately solidifying within a cumulus rock.

Biological weathering is a function of biotic energy expenditure. Growth and metabolism of organisms generates acids and chelators, selectively absorbs nutrient ions, and applies turgor pressure and other physical forces which, in concert, chemically and physically alter minerals. In unsaturated soil environments, plant roots normally form symbiotic mycorrhizal associations with fungi. The plants provide photosynthate-carbohydrate-energy to the fungi in return for nutrients absorbed from the soil and released from minerals. In ectomycorrhiza, one of the two major types of mycorrhiza of trees, roots are sheathed in fungus, and 15—30% of the net photosynthate of the plants passes through these fungi into the soil and virtually all of the water and nutrients taken up by the plants are supplied through the fungi. Here we show that ectomycorrhizal fungi actively forage for minerals and act as biosensors that discriminate between different grain sizes (53—90 μm, 500—1000 μm) and different minerals (apatite, biotite, quartz) to favour grains with a high surface-area to volume ratio and minerals with the highest P content. Growth and carbon allocation of the fungi is preferentially directed to intensively interact with these selected minerals to maximize resource foraging.

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.

Apatite samples from rare-metal mineralization were investigated by a combination of cathodoluminescence (CL) microscopy and spectroscopy, microchemical analysis and trace element analysis. Internal structures revealed by CL can be related to variations in the crystal chemistry and may sometimes reflect changes in the composition of the mineralizing fluids.

Apatite from mineralization related to alkaline rocks and carbonatites (Type 1) typically exhibits relatively homogeneous blue and lilac/violet CL colours due to activation by trace quantities of rare earth element ions (Ce3+, Eu2+, Sm3+, Dy3+ and Nd3+). These results correlate with determined trace element abundances, which show strong light rare earth element (LREE) enrichment for this type of apatite. However, a simple quantitative correlation between emission intensities of REE3+/2+ and analysed element concentrations was not found.

Apatite from P-rich altered granites, greisens, pegmatites and veins from Sn-W deposits (Type 2) shows strong Mn2+-activated yellow-greenish CL, partially with distinct oscillatory zoning. Variations in the intensity of the Mn2+-activated CL emission can be related either to varying Mn/Fe ratios (quenching of Mn activated CL by Fe) or to self-quenching effects in zones with high Mn contents (>2.0 wt.%). The REE distribution patterns of apatite reflect the specific geological position of each sample and may serve as a “tracer” for the REE behaviour within the ore system. Although the REE contents are sometimes as high as several hundred parts per million, the spectral CL measurements do not exhibit typical REE emission lines because of dominance of the Mn emission. In these samples, REE-activated luminescence is only detectable by time-resolved laser-induced luminescence spectroscopy.

Both types of apatite (Type 1 in the core and Type 2 in the rim) were found in single crystals from the Be deposit Ermakovka (Transbaikalia). This finding proves the existence of two stages of mineralization within this deposit.

The application of ion microprobe analysis to REE determination is discussed, with special reference to REE-bearing accessory minerals (e.g. allanite, monazite, apatite, xenotime, sphene). The main analytical problems are shown to be (a) interferences in the mass spectrum caused by molecular ions, and (b) matrix effects, i.e. variations in ion yield with sample composition. Interference suppression using either high mass resolution or secondary-ion energy discrimination is fairly effective, but entails a significant sacrifice in peak intensity. In the absence of a viable model for predicting matrix effects, it is proposed that empirical standardization should be used. Often better absolute accuracy can be obtained by combining ion microprobe and electron microprobe data for REE present in sufficiently high concentrations. Detection limits for REE are in the part per million region at present, with spatial resolution typically around 10 μm, but there is considerable scope for improvement. Better standards and improved understanding of matrix effects should also lead to greater accuracy in quantitative analysis.

A carbonatite sample from Phalaborwa, South Africa, consists of apatite, magnetite and a calcitedolomite ‘perthite’ which is interpreted as being due to exsolution of dolomite from a high-Mg calcite precursor. Carbon and oxygen isotope data indicate that the carbonates are equilibrated. In situ ionmicroprobe analyses for Fe, Mn, Na, Si, Y, the REEs, Pb, Th and U give the following average concentrations (in ppm) in the sequence apatite, calcite, dolomite: Fe 98, 1680, 8190; Mn 61, 510, 615; Na 1171, 627, 125; Si 368; 1.6, 0.2; Sr 4447, 5418, 2393; Ba 37, 2189, 75; La 1245, 300, 67; Y 121, 50, 5.8; Pb 16, 5.4, 1.4; Th 20, 0.02, 0; U 2.4, 0, 0.01. The concentrations are reasonably uniform in both apatite and dolomite, but in calcite are more variable. Na, Si, Y, the REEs, Pb, Th and U partition into apatite relative to both carbonates (and, hence, the precursor carbonate); KD ap/cc for REE decreases from ∽4 for La to ∽2 for Tm. There is almost equal partitioning of Sr between apatite and calcite. During separation of dolomite from calcite, Sr and Ba partition strongly into calcite and all the other analysed elements, except Fe and Mn, also preferentially enter calcite. The REEs prefer calcite relative to dolomite, and the KD dol/cc is reasonably constant, only varying from 0.23 to 0.17. Sr, Ba and Pb in the carbonates, and their partitioning between the calcite and dolomite, differ from other carbonatite carbonates reported in the literature.

Published electron microprobe analyses of mattheddleite, a lead sulpho-silicate apatite from Leadhills, Scotland, have 9–13% IV site deficiencies. However, galena was used as a standard for S, which suggested that low S resulted from a shift in the S-Kα peak. Wavelength scans with a PET crystal show that the S-Kα peak is shifted down by 0.0026 Å for sulphates relative to sulphides. Quantitative analyses show a ∼30% increase of S in mattheddleite using a celestite standard, which fills the IV site, but with Si > S, on average Pb5S1.2Si1.8O11.7Cl0.6(OH)0.4. Direct analysis of oxygen with the electron microprobe implies that the charge imbalance engendered from the inequality of Si and S is compensated with substitution of a vacancy (□), as in Pb5S1.2Si1.8[O11.7□0.3] [Cl0.6(OH)0.4] or Pb5S1.2Si1.8[O11.7(Cl, OH)0.73]. [Cl,OH)0.7 □0.3]. Calculation of OH as l–C1 suggests the presence of both OH- and Cl-dominant mattheddleite at Leadhills, but direct analysis of H is needed to confirm the dominance of OH in the channel site. Wavelength-dispersive analyses of S in apatite and other sulphates must be undertaken with sulphate standards: use of sulphide standards yields a negative error on the order of 10–20% in the resultant S concentration. Reactions of mattheddleite with other Pb minerals at Leadhills show that their stability depends on fluid composition as well as pressure and temperature. An X-ray map of Cl shows complex zoning between Cl-poor and Cl-rich mattheddleite, recording rapid changes in the fluid chemistry during late-stage hydrothermal processes at Leadhills.