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Weathered granite of ion-adsorption rare earth elements (REEs) ore collected at Jiangxi Province, China was investigated to identify the minerals abundant in REEs. The analyses of scanning electron microscopy (SEM)-energy dispersive spectrometry (EDS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for individual mineral particles of the weathered granite showed that kaolinitic particles formed by K-feldspar weathering contained large amounts of REEs. Scanning transmission electron microscopy (STEM)-EDS analyses revealed that the kaolinitic particles were mainly composed of kaolinite, illite and hematite. The elemental maps by Nano-SIMS for the kaolinitic particle clarified that La and Y are particularly concentrated in illite. The presence of illite presumably contributes to the formation of the REE accumulation zone in weathered granite. Furthermore, in the in-situ desorption experiment, nearly half the REEs (45.5%) remained in the kaolinitic particle after the treatment with 0.5 M ammonium sulfate solution. The desorption ratio of heavy REEs (HREEs: Gd–Lu) (60.4%) was lower than that of light REEs (LREEs: La–Eu) apart from Ce (69.0%). These results suggest that REEs form inner-sphere complexes on the kaolinitic particle. It can be assumed that the inner-sphere complexation suppresses the extraction ratio of REEs from the ores by ion-exchange treatment.

Background Symbiosis is central to ecosystems and has been an important driving force of the diversity of life. Close and long-term interactions are known to develop cooperative molecular mechanisms between the symbiotic partners and have often given them new functions as symbiotic entities. In lichen symbiosis, mutualistic relationships between lichen-forming fungi and algae and/or cyanobacteria produce unique features that make lichens adaptive to a wide range of environments. Although the morphological, physiological, and ecological uniqueness of lichens has been described for more than a century, the genetic mechanisms underlying this symbiosis are still poorly known. Results This study investigated the fungal-algal interaction specific to the lichen symbiosis using Usnea hakonensis as a model system. The whole genome of U. hakonensis, the fungal partner, was sequenced by using a culture isolated from a natural lichen thallus. Isolated cultures of the fungal and the algal partners were co-cultured in vitro for 3 months, and thalli were successfully resynthesized as visible protrusions. Transcriptomes of resynthesized and natural thalli (symbiotic states) were compared to that of isolated cultures (non-symbiotic state). Sets of fungal and algal genes up-regulated in both symbiotic states were identified as symbiosis-related genes. Conclusion From predicted functions of these genes, we identified genetic association with two key features fundamental to the symbiotic lifestyle in lichens. The first is establishment of a fungal symbiotic interface: (a) modification of cell walls at fungal-algal contact sites; and (b) production of a hydrophobic layer that ensheaths fungal and algal cells;. The second is symbiosis-specific nutrient flow: (a) the algal supply of photosynthetic product to the fungus; and (b) the fungal supply of phosphorous and nitrogen compounds to the alga. Since both features are widespread among lichens, our result may indicate important facets of the genetic basis of the lichen symbiosis.

The analytical efficacy of five gas mixers and five stabilizers on signal stabilization and washout time obtained for laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) was evaluated in the present study. In the case of gas mixers examined, a total of 95 patterns of their attitudes as well as different directions of the gas flows were examined, and it was found that the signal variation and the washout time were strongly dependent on these factors. Even in a simple Y-shaped fitting (Y-mixer), signal stability and washout time had large variations with respect to its different attitudes as well as gas flow directions. The shortest washout time for each gas mixer was almost the same ranging from 1.0 to 1.2 s. The signal variations observed were 11-15% of relative standard deviation (RSD) under optimum conditions for each gas mixer. The optimum condition of a Y-mixer for LA-ICPMS represented 11% RSD and 1.0 s for signal variation and washout time, respectively. In the case of stabilizers examined, almost all stabilizers improved signal variations from 11 to 3.0-9.3%, but washout times became longer than those of the only Y-mixer from 1.0 to 1.2-8.9 s. The important thing is that the signal stability and the washout time are trade-off correlations for gas mixers and stabilizers. A suitable gas mixer or a stabilizer on the trade-off line can be selected with respect to different applications. It was also observed that variations of both signal stability and washout time correlated with the volume of stabilizers despite their different inner structures; that is, a stable signal and longer washout time seemed to be observed when the volume of the chamber became larger. This suggested that the signal stabilization obtained by stabilizers was ascribable to not only elimination of larger particles from laser ablation but also particle mixing effect, which compensated signal variation.

Spherical radioactive caesium (Cs)-bearing microparticles (CsMPs) were emitted during the Fukushima Dai-ichi Nuclear Power Plant (FDNPP) accident in March, 2011. The emission source (timing) and formation process of these particles remain unclear. In this study, the isotopic ratios of uranium (235U and 238U) and caesium (133Cs, 134Cs, 135Cs, and 137Cs) isotopes in the five spherical CsMPs (ca. 2 μm in size) sampled at 50 km west of the FDNPP were determined using secondary ion mass spectrometry and laser ablation-ICPMS, respectively. Results showed that the 235U/238U ratios of CsMPs were homogeneous (1.93 ± 0.03, N = 4) and close to those estimated for the fuel cores in units 2 and 3, and that the Cs isotopic ratios of CsMP were identical to those of units 2 and 3. These results indicated that U and Cs in the spherical CsMPs originated exclusively from the fuel melt in the reactors. Based on a thorough review of literatures related to the detailed atmospheric releases of radionuclides, the flow of plumes from the FDNPP reactor units during the accident and the U and Cs isotopic ratio results in this study, we hereby suggest that the spherical CsMPs originate only from the fuel in unit 2 on the night of 14 March to the morning of 15 March. The variation range of the analysed 235U/238U isotopic ratios for the four spherical particles was extremely narrow. Thus, U may have been homogenised in the source through the formation of fuel melt, which ultimately evaporating and taken into CsMPs in the reactor and was released from the unit 2.

The mass transfer of additive elements during the sintering of barium titanate (BaTiO3) ceramic was examined by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) in the present study. An analytical sample consisting of two pellets of BaTiO3 with different concentrations of additive elements of manganese (Mn) and holmium (Ho) as well as silicon (Si) as a sintering reagent was prepared and measured by LA-ICP-MS with small laser irradiated diameter of 10 μm to evaluate the distributions and concentrations of additive elements in order to examine their mass transfers. As results, enrichments of Mn and Si as an additive element and a sintering reagent, respectively, were observed on the adhesive surface between two BaTiO3 pellets, even though Ho did not show a similar phenomenon. The mass transfers of additive elements of Mn and Ho were also examined, and Mn seemed to show a larger mass transfer than that of Ho during the sintering process for BaTiO3 ceramics. The results obtained in this study shows the effectives of LA-ICP-MS for the future improvement of MLCCs.

The Hida Belt, central Japan, is a continental fragment, which was once a part of the crustal basement of the East Asian continental margin. It consists mainly of Permo-Triassic granite-gneiss complexes with both syn-to-late-metamorphic migmatite or granite bodies. Clinopyroxene-bearing leucogranite, locally called as ‘Inishi’-type migmatite, occurs characteristically in the migmatite zone associated with amphibolite and marble. The leucogranite is characterized by the presence of coarse-grained diopside–hedenbergite series clinopyroxene and titanite in plagioclase-dominated matrix. Clinopyroxene contains abundant calcite inclusions. Euhedral titanite with high Th/U ratios (~2.8–7.8) and REE contents (~4514–14,069 μg/g) contains polycrystalline ‘granitic’ inclusions. Those mineralogical features indicate the involvement of carbonate during anatexis. Considering a nominal pressure of 0.4–0.7 GPa of the Hida gneiss, Zr-in-titanite thermometry yields a temperature of 730–810 °C and 770–850 °C at aTiO2 = 0.5 and 1, respectively. The titanites show highly variable U/Pb (238U/206Pb = 15.0–24.0) and Pb (207Pb/206Pb = 0.172–0.419) isotope ratios, and the scattered trend follows a discordia line with a lower intercept at 225.4 ± 1.9 Ma. This titanite age would represent the timing of regional anatexis that have occurred in a later stage of the regional metamorphism of the Hida Belt. A high apparent thermal gradient at middle crustal levels might have been caused by regional extension.

The Benjamin River apatite prospect in northern New Brunswick, Canada, is hosted by the Late Silurian Dickie Brook plutonic complex, which is made up of intrusive units represented by monzogranite, diorite and gabbro. The IOA ores, composed mainly of apatite, augite, and magnetite at Benjamin River form pegmatitic pods and lenses in the host igneous rocks, the largest of which is 100 m long and 10–20 m wide in the diorite and gabbro units. In this study, 28 IOA ore and rock samples were collected from the diorite and gabbro units. Mineralogical observations show that the apatite–augite–magnetite ores are variable in the amounts of apatite, augite, and magnetite and are associated with minor amounts of epidote-group minerals (allanite, REE-rich epidote and epidte) and trace amounts of albite, titanite, ilmenite, titanomagnetite, pyrite, chlorite, calcite, and quartz. Apatite and augite grains contain small anhydrite inclusions. This suggests that the magma that crystallized apatite and augite had high oxygen fugacity. In back scattered electron (BSE) images, apatite grains in the ores have two zones of different appearance: (i) primary REE-rich zone; and (ii) porous REE-poor zone. The porous REE-poor zones mainly appear in rims and/or inside of the apatite grains, in addition to the presence of apatite grains which totally consist of a porous REE-poor apatite. This porous REE-poor apatite is characterized by low REE (

Ion adsorption rare earth element (REE) deposits in southern China are the exclusive source of heavy REEs (HREEs) in the world, and this HREE-enriched character of the deposits is inherited from the REE compositions of the underlying granitic rocks. Such HREE-enriched rocks form from heavy fractionation of reduced granitic magmas. We explore why reduced granitic magmas are enriched in HREEs during the fractionation, based on the REE geochemistry of granitic rocks and abundance of REEs in their constituent minerals in the southwestern Japan arc of Cretaceous to Paleogene age. The compilation of the whole rock geochemistry and REE compositions of the granitic rocks of the Sanin (oxidized), Sanyo (reduced) and Ryoke (reduced) belts in the southwestern Japan arc indicates that: (i) light REEs (LREEs) decease with fractionation of the granitoids in the Sanin belt but this trend is not clear in the granitoids in the Sanyo belt and LREEs rather increase in the Ryoke granitoids; (ii) Eu decreases with fractionation in all the belts; and (iii) HREEs slightly, but steadily decrease in the Sanin belt but enrich significantly in the Sanyo and Ryoke belts with fractionation. Analytical results of REE concentrations by scanning electron microscope with energy dispersive X-ray spectroscope and laser ablation-inductively coupled plasma mass spectrometer in the constituent minerals in a granodiorite sample from the Sanin belt show a moderate concentration of REEs in hornblende (577 ppm) in addition to high concentrations in allanite (~20 %), britholite (~30 %), primary titanite (8922 ppm), apatite (4062 ppm), and zircon (1693 ppm). Because primary titanite and allanite are commonly present in the oxidized granitoids but not in the reduced ones, the REE depletion in the fractionated, oxidized granites is attributed to the crystallization of these minerals. In contrast, scarcity of these minerals in the reduced granitoids enriches REEs, in particular HREEs in the fractionated magmas, which finally precipitate REEs in the granites and pegmatites. Both positive, but different correlation ratios between the Nb and Dy concentrations in the granitoids of the Sanin and Sanyo-Ryoke belts suggest that columbite–pyrochlore-group and fergusonite-group minerals are the major HREE host in the oxidized and reduced granites, respectively.

The oxidation states of Fe within olivine, orthopyroxene, clinopyroxene, and spinel in a spinel lherzolite xenolith from the Tariat Depression, Mongolia were investigated using 57Fe Mössbauer spectroscopy to evaluate the redox condition of the upper mantle from which the Tariat spinel lherzolite xenolith was derived. The purity of separated minerals for the Mössbauer spectroscopic analysis was examined using X-ray powder diffraction, Raman spectroscopy, and transmission electron microscopy. Average Fo and Fe contents of olivine at the core part of the xenolith are 89.9(4) mol % and 0.195(3) atoms per formula unit, respectively. The Fe3+/ΣFe values of the olivine, orthopyroxene, clinopyroxene, and spinel, determined by Mössbauer spectroscopic analysis, are 0.027(2), 0.15(1), 0.26(3), and 0.34(5), respectively. The Mössbauer spectrum of olivine consists of two doublets assigned to Fe2+ at the octahedral sites and one doublet, with I.S. of 0.40(2) mm/s and Q.S. of 0.69(3) mm/s assigned to Fe3+ at the octahedral site. Since the Tariat spinel lherzolite xenolith in this study shows no evidence of metasomatism or thermal alteration, the existence of a small amount of Fe3+ in olivine and the fairly high Fe3+ contents of clinopyroxene, orthopyroxene, and spinel imply that the upper mantle under the Tariat area was in a rather oxidized condition.

Geochemical compositions are reported for Late Miocene to Pliocene granitoids from the Taitao Peninsula near the Chile ridge subduction zone. Major element compositions of Taitao granitoids show a resemblance with those of TTG suites. However, trace element compositions are characterized by low Sr (50‐300 ppm), moderately high Y (10‐45 ppm) and Yb concentrations (1‐5 ppm), and low Sr/Y and La/Yb ratios compared with those of typical adakites, which are presumably produced by melting of young and hot oceanic crust under eclogite to garnet amphibolite conditions. Instead, trace element composition of the Taitao granitoids resembles that of typical calc‐alkaline arc magmas. Based on trace element compositions, together with tectonic constraints, we infer that the Taitao granitoids were generated by partial melting of the subducted oceanic crust in garnet-free amphibolite conditions at depths shallower than 30 km. Our results indicate that slab-melting-related magmas do not necessarily show a HREE-depleted signature, which was used as evidence for slab-melting for granitic rocks of the TTG suites.

Zircon (ZrSiO4) from Naegi and Ohro granitic pegmatites, Japan and from Saigon alkali basalt, Vietnam, were mineralogically characterized by inductively couples plasma mass spectrometry (ICP-MS), electron-microprobe analysis (EMPA), X-ray powder diffraction, micro-Raman spectroscopy and leaching experiment. The powder XRD and Raman spectra analyses show that the degree of metamictization increases in the following order: Saigon (crystalline), Ohro (partly metamict) and Naegi zircons (fully metamict). Quantitative analytical results by the EMPA indicate that the Naegi and Ohro zircon samples contain a large amount of REE2O3, while REE2O3 contents in Saigon zircon are below detection limit. The leaching experiments using a solvent 1 M-HCl for the present zircons under the condition at a room temperature to 250 °C and retention time of 30 h resulted in about 100%, 50% and 1% recoveries of REE from the Naegi, Ohro and Saigon zircons, respectively. Leaching experiments for the Naegi zircon at different temperatures and retention time 30 h, showed that a significant amount of REE was leached out at the temperature above 150 °C, although REE were hard to be leached at a room temperature (about 25 °C). Therefore, both low crystallinity of zircon and higher leaching temperature are requisite for effective leaching of REE from zircon.

Using laser-ablation inductively coupled plasma mass spectrometer (LA-ICPMS), we have improved the reliability of the abundance data for trace-elements in geochemical samples using a glass bead ablation method. The glass beads were made of mixture of 0.1 g sample and 1.0 g of lithium-tetraborate preliminary prepared for an analysis of major components using a X-ray fluorescence (XRF) technique. The present method has several advantages: 1) higher sensitivity than that achieved by the XRF method, 2) obviation of erroneous measurements due to incomplete dissolution of heavy minerals, and 3) simple, rapid and user friendly sample preparation procedures for the analysis of both the major and trace elements. Development of this method constitute: 1) femtosecond laser-ablation for minimal elemental fractionation during the laser ablation, 2) new software to control all the laser, sample stage movement as well as triggering the data acquisition using the ICP-MS, and 3) a newly designed sample cell to enhance the transport efficiency of the sample aerosol into the ICP. Moreover, to improve the data quality for both the major and trace elements, calibration lines were defined based on the Li-normalized signal intensities and the reported abundance values for the analytes in well distributed GSJ geochemical reference samples. These improvements enabled us to analyze whole-rock compositions at ≤100 sec/sample. Using this method, the precisions of analyses were better than 10% for Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Mn, Co, Ga, Rb, Sr, Y, Zr, Nb, La, Pr and Nd; 20% for P, Zn, Sn, Ce, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, Th, and U, and 30% for Fe, Cs, Ba, and Eu. For Ni and As, precisions of the measurements was not better than 30%. Reliabilities of analyses were better than 10% for Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Mn, Co, Rb, Sr, Y, Zr, Cs, Ba, La, Ce, Nd, Sm, Gd, Tb, Dy, Yb, Lu, Hf, Th and U

application/pdf, The Taitao granites are distributed around the Late Miocene Taitao ophiolite (5.66 ± 0.33 Ma to 5.19 ± 0.15 Ma) exposed at the western tip of the Taitao peninsula, southern Chile, ~ 50 km southeast from the present day Chile triple junction. In this paper, we report sensitive high mass-resolution ion microprobe (SHRIMP) U–Pb ages for the Taitao granites to elucidate the temporal relationship between the ophiolite and granites, and discuss the origin of the granitic melts. Five intrusive bodies of the Taitao granites have U–Pb ages ranging from 5.70 ± 0.25 Ma (Tres Montes pluton in southeast) to 3.92 ± 0.07 Ma (Cabo Raper pluton in southwest). The Estero Cono, Seno Hoppner and Bahia Barrientos intrusions that fringe eastern margin of the ophiolite have U–Pb ages ranging from 5.17 ± 0.09 Ma to 4.88 ± 0.3 Ma. Recycled zircon cores are common only in the Tres Montes pluton. Our data indicate that the generation of the granitic melts started in the Tres Montes area when a short segment of the Chile ridge system started to subduct ca. 6 Ma ago. This magmatism involved contamination with sediments/basement rocks. A part of the subducting ridge center was emplaced to form the present Taitao ophiolite at ~ 5.6 Ma. Generation of granitic melts continued as the spreading center of the same ridge segment subducted, due perhaps to partial melting of the ophiolite and/or oceanic crust enhanced by heat from upwelling mantle beneath the ridge. Granitic magmas with various compositions developed during subduction of the ridge. Emplacement of the ophiolite and formation of continental crust took place almost simultaneously.

Orthopyroxene-clinopyroxene-plagioclase needles and symplectite along the cleavage planes and grain boundaries of fluorine-bearing titanian-ferroan pargasite from the Highland Complex, Sri Lanka, are interpreted as evidence for dehydration melting at ultrahigh-temperature conditions. High Ti (up to 0.4 pfu) and F ( X F up to 0.56) content in pargasite extends its stability to higher temperatures, and the composition indicates the dehydration melting reaction may take place at ultrahigh-temperatures (~950 °C) at a pressure around 10 kbar, close to peak metamorphic conditions. The increase of Ti content close to the grain boundaries and cleavage planes in pargasite indicates titanium partitioning from the melt during dehydration melting enhanced the stability of the mineral toward ultrahigh-temperature conditions. The REE content in the pargasite shows a similar behavior to that of titanium. The cores with no breakdown assemblage consist of low and flat REE concentrations with respect to the high and Eu-depleted rim. Clinopyroxene in symplectite and needle-shaped lamellae within the pargasite porphyroblasts have similar REE patterns with slightly low-concentrations relative to that of pargasite. In the breakdown assemblage, LREEs are partitioned mainly into plagioclase while the HREEs are partitioned into orthopyroxene. The REE enrichment in the pargasite rims signals their relative partitioning between pargasite rims and melt. Modeling of the partitioning of Ti and REEs associated with pargasite breakdown demonstrates that its stability is greatly enhanced at UHT conditions. This investigation implies that the stability of hydrous minerals such as amphibole can be extended to UHT conditions, and expands our knowledge of metamorphism in the lower crust.

A laser ablation-inductively coupled plasma-mass spectrometric (LA-ICPMS) technique utilizing a titanium-sapphire (TiS) femtosecond laser (fs-laser) has been developed for elemental and isotopic analysis. The signal intensity profile, depth of the ablation pit and level of elemental fractionation were investigated in order to evaluate the analytical capability of the present fs-laser ablation-ICPMS technique. The signal intensity profile of (57)Fe, obtained from iron sulfide (FeS(2)), demonstrated that the resulting signal intensity of (57)Fe achieved by the fs-laser ablation was almost 4-times higher than that obtained by ArF excimer laser ablation under a similar energy fluence (5 J/cm(2)). In fs-laser ablation, there is no significant difference in a depth of the ablation pit between glass and zircon material, while in ArF laser ablation, the resulting crater depth on the zircon crystal was almost half the level than that obtained for glass material. Both the thermal-induced and particle size-related elemental fractionations, which have been thought to be main sources of analytical error in the LA-ICPMS analysis, were measured on a Harvard 91500 zircon crystal. The resulting fractionation indexes on the (206)Pb/(238)U (f(Pb/U)) and (238)U/(232)Th (f(U/Th)) ratios obtained by the present fs-laser ablation system were significantly smaller than those obtained by a conventional ArF excimer laser ablation system, demonstrative of smaller elemental fractionation. Using the present fs-laser ablation technique, the time profile of the signal intensity of (56)Fe and the isotopic ratios ((57)Fe/(54)Fe and (56)Fe/(54)Fe) have been measured on a natural pyrite (FeS(2)) sample. Repeatability in signal intensity of (56)Fe achieved by the fs-laser ablation system was significantly better than that obtained by ArF excimer laser ablation. Moreover, the resulting precision in (57)Fe/(54)Fe and (56)Fe/(54)Fe ratio measurements could be improved by the fs-laser ablation system. The data obtained here clearly demonstrate that, even with the fundamental wavelength (NIR operating at 780 nm), the fs-laser ablation system has the potential to become a significant tool for in-situ elemental and isotopic analysis of geochemical samples including heavy minerals and metallic materials.