Search

Using the Rock Canyon Creek carbonate-hosted rare earth element (REE)–F–Ba deposit as an example, we demonstrate the need for verifying inherited geochemical data prior to reinterpretation. Inherited La, Ce, Nd and Sm data obtained by pressed pellet X-ray fluorescence (XRF), and La and Y data obtained by aqua regia digestion inductively coupled plasma atomic emission spectroscopy (ICP-AES) for more than 300 drill-core samples were analysed in 2009 and were subsequently compared to sample subsets re-analysed using lithium metaborate-tetraborate (LMB) fusion ICP mass spectroscopy (ICP-MS), Na2O2 fusion ICP-MS, and LMB fusion-XRF. We determine that LMB ICP-MS and Na2O2 ICP-MS accurately determined REE concentrations in control reference materials (CRM) SY-2 and SY-4, and provided precision of about 10%. Fusion-XRF was precise for La, Ce and Nd at concentrations greater than ten times the lower detection limit; however, accuracy of this method was not established because REE concentrations in SY-4 were below the lower detection limit. Analysis of the sample subset revealed substantial discrepancies for Ce concentrations determined by pressed pellet XRF in comparison to those determined by other methods due to Ba spectral interference. Samarium, present in lower concentrations than other REE that were determined, was consistently underestimated by XRF methods relative to ICP-MS methods. This may be the result of Sm concentrations approaching the lower detection limits of XRF methods, elemental interference or inadequate background corrections. Aqua regia dissolution results, reporting only for La and Y, are underestimated relative to the other methods. We highlight the importance of selecting the most appropriate analytical method and reference materials for determining the REE content of mineralized rock which may be several orders of magnitude higher than that of typical host rock.

Background Immobilization in external rotation after a first-time shoulder dislocation was introduced to reduce the risk of recurrence compared to immobilization in internal rotation, but its efficacy remains controversial. The purpose of this study was to determine the long-term effect of immobilization in external rotation after a first-time shoulder dislocation. Methods Between October 2000 and March 2004, 198 patients with a first-time anterior dislocation of the shoulder (average age 28) were randomly assigned to immobilization in external rotation (ER group = 104 shoulders) or internal rotation (IR group = 94 shoulders) for 3 weeks. At an average 2-year follow-up, 159 patients (80.3%) were available for evaluation. In the current study, these 159 patients were further followed up and interviewed by telephone. The following items were evaluated: recurrent instability, apprehensive feeling, surgical intervention, limitation in the range of motion, return to sports, and the single assessment numeric evaluation (SANE) score. Results The average follow-up period was 18.2 years (range, 16 – 20 years). Fifty-six patients were available for follow-up with the follow-up rate of 35%. The recurrent patients were 6/27 (22%) in the ER group and 6/29 (21%) in the IR group (p = 0.889). The surgically stabilized patients were 3/27 (11%) in the ER group and 10/29 (34%) in the IR group (p = 0.038). In total, the recurrence rate was 9/27 (33%) in the ER group and 16/29 (55%) in the IR group (p = 0.100). Adding the surgical cases and those with the SANE score ≤ 70% as failure cases, the failure rate was significantly lower in the ER group (26%) than in the IR group (52%) (p = 0.048). Among those who survived without surgical intervention, there were no significant differences in apprehensive feeling, return to sports, limited range of motion, and the SANE score between the groups. Conclusions Immobilization in external rotation reduced the risk of surgical intervention compared to internal rotation in the long-term.

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 (

Provenance analysis and U–Pb dating of detrital zircons in Permian–Triassic forearc sediments from the Sukhothai Arc in northern Thailand clarify the evolution of a missing arc system associated with Paleo-Tethys subduction. The turbidite-dominant formations within the forearc sediments include the Permian Ngao Group (Kiu Lom, Pha Huat, and Huai Thak formations), the Early to earliest Late Triassic Lampang Group (Phra That and Hong Hoi formations), and the Late Triassic Song Group (Pha Daeng and Wang Chin formations). The sandstones are quartzose in the Pha Huat, Huai Thak, and Wang Chin formations, and lithic wacke in the Kiu Lom, Phra That, Hong Hoi and Pha Daeng formations. The quartzose sandstones contain abundant quartz, felsic volcanic and plutonic fragments, whereas the lithic sandstones contain mainly basaltic to felsic volcanic fragments. The youngest single-grain (YSG) zircon U–Pb age generally approximates the depositional age in the study area, but in the case of the limestone-dominant Pha Huat Formation the YSG age is clearly older. On the other hand, the youngest cluster U–Pb age (YC1σ) represents the peak of igneous activity in the source area. Geological evidence, geochemical signatures, and the YC1σ ages of the sandstones have allowed us to reconstruct the Sukhothai arc evolution. The initial Sukhothai Arc (Late Carboniferous–Early Permian) developed as a continental island arc. Subsequently, there was general magmatic quiescence with minor I-type granitic activity during the Middle to early Late Permian. In the latest Permian to early Late Triassic, the Sukhothai Arc developed in tandem with Early to Middle Triassic I-type granitic activity, Middle to Late Triassic volcanism, evolution of an accretionary complex, and an abundant supply of sediments from the volcanic rocks to the trench through a forearc basin. Subsequently, the Sukhothai Arc became quiescent as the Paleo-Tethys closed after the Late Triassic. In addition, parts of sediments of supposed Devonian–Carboniferous age within the Sukhothai Arc were revised as the Triassic Lampang Group, and the Early Cretaceous Khorat Group.

This study analyzes the Thermoluminescence (TL) emissions for five emission bands, trace element concentrations and defects in quartz grains extracted from metamorphic rocks and quartz veins in the Sambagawa metamorphic belt, central Shikoku. An emission of 500 nm with 195, 245, and 320–325 °C glow peaks are observed through the lowest to highest grade samples. A 450 nm emission band with intense 195 and 245 °C glow peaks and a 320–325 °C shoulder peak is found in the higher grade samples. A 570 nm emission band with a 170 °C glow peak is observed in the samples derived from the lower grade zones. These characteristics of TL emissions of quartz suggest that they can be an indicator for the identification of rock derived from different metamorphic grades. The higher metamorphic grade samples with 450 nm emission bands in particular show higher intensities of the E1′ center. This relation indicates that the activation of the E1′ center in higher metamorphic conditions possibly contributed to the 450 nm emission band. Also, the 500 nm emission band is generally observed in the samples with the signal intensities of the Aluminum hole center, suggesting that the center is the source of this emission band. We also observed that the lower metamorphic grade samples contain lower signal intensities of the Aluminum hole center, despite higher aluminum concentrations. This inconsistency indicates that the formation of interstitial aluminum ions cause local lattice distortion regions, where self-trapped excitons can be formed and presumably provide the 570 nm emissions.

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.

Apatite, which is used in the production of phosphorus fertilizers, contains small amounts of rare earth elements (REEs; 0.1–1%). Apatite deposits occur all over the world and thus have the potential to be a secure source of REEs. We investigated a method for recovery of REEs from an apatite sample; specifically, REEs were leached from the sample with an H2SO4 solution, the acid that is most commonly used for fertilizer production. At high H2SO4 concentrations, most of the REEs in the solution were lost to precipitation as insoluble gypsum (CaSO4·2H2O). However, at H2SO4 concentrations of

Geochemical characteristics and rare-earth element (REE)-bearing minerals of calc-alkaline granites in southern Myanmar were investigated to identify the minerals controlling fractionation between light and heavyREE(LREE and HREE) during magmatic differentiation and weathering. The granites were classified on the basis of the mineral assemblages into two contrasting groups: allanite-(Ce)- and/or titanite-bearing granites; and more HREE-enriched granites characterized by hydrothermal minerals including synchysite(Y), parisite-(Ce), bastnäsite-(Ce), xenotime-(Y), monazite-(Ce), Y-Ca silicate, waimirite-(Y) and fluorite. This suggests that allanite-(Ce) and titanite are not stable in differentiated magma and HREE are eventually preferentially incorporated into the hydrothermal minerals. The occurrence of theREE-bearing minerals is constrained by the degree of magmatic differentiation and the boundary of two contrasting granite groups is indicated by SiO2contents of ∼74 wt.% or Rb/Sr ratios of ∼3–8. Fractionation between LREE and HREE during weathering of the granites is influenced by weathering resistance of theREE-bearing minerals, i.e. allanite-(Ce), titanite, theREEfluorocarbonates and waimirite-(Y) are probably more susceptible to weathering, whereas zircon, monazite-(Ce) and xenotime-(Y) are resistant to weathering. Ion-exchangeableREEin weathered granites tend to be depleted in HREE relative to the whole-rock compositions, suggesting that HREE are more strongly adsorbed on weathering products or that HREE remain in residual minerals.

To explore the influence of radioactive heavy minerals on thorium (Th) and uranium (U) contamination in groundwater, we performed geochemical and mineralogical investigations of core samples (from ...

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.

The Permo-Jurassic North Thai (NT) Granites and the Late Cretaceous to Paleogene Western Province (WP) Granites in Thailand are contrasting in terms of tectonic settings and chemical compositions. The NT Granites, which are dominated by S-type features, are characterized by lower SiO2 contents and higher P2O5 contents than the WP Granites in this study. In order to compare the mobility and adsorption of rare earth elements (REEs) during weathering of the two granite suites, geochemical analyses were conducted on the granite and weathered granites. The weathered WP Granites show wider ranges of REEs + Y (REY) contents, percentages of ion-exchangeable REY and Ce anomalies than the weathered NT Granites. These results indicate that REEs were less mobile during weathering of the NT Granites than those of the WP Granites. The low mobility of REEs can be explained by the occurrences of residual monazite and secondary REE phosphates which immobilize REEs during weathering. Therefore, in the weathered NT Granites, REEs are mostly contained in the phosphate minerals. In contrast, the weathered WP Granites are dominated by ion-exchangeable REEs (adsorbed REEs) which are likely to exist on the surface of clays. Previous studies and our study results suggest that the ion-exchangeable REEs in the weathered granites were probably sourced from weatherable allanite, titanite, apatite and/or REE fluorocarbonate, and rarely from monazite and zircon, which are resistant to weathering. The weathered granites of low phosphate contents potentially show high percentages of ion-exchangeable REY, although they can be influenced by the degree of hydrothermal alteration or weathering of granites.

Rodingites occur in serpentine-matrix melange of the Nagasaki metamorphic rocks in Japan. Two types of rodingites can be distinguished on the basis of their mode of occurrence and mineralogical composition. One occurs as dikes, which contain a mineral assemblage of grossular, vesuvianite, diopside, apatite, titanite, and zircon. The other occurs as a block, which consists of zoisite, clinozoisite, diopside, chlorite, apatite, titanite, and zircon. The former type of rodingites posses two types of zircons: prismatic and porous. The prismatic zircons contain primary fluid inclusions indicating their crystallization in the presence of fluids. The porous zircons have extensive fractures filled by zircon, which are indicative of a hydrothermal origin. Both zircon types were thought to have formed under the influence of fluids. U–Pb ion probe analyses of prismatic zircons from the rodingites yield a weighted mean age of 108–105 Ma, suggesting the Early Cretaceous as the time of rodingitization in the subduction zone. Hafnium isotopic compositions of prismatic zircons are close to or overlap with the mid ocean ridge basalt (MORB) Hf isotopic ratio. This indicates that the fluid composition may have been reflected by the MORB composition during rodingitization. On the other hand, the low eHf values (11.8–18.9) of porous zircons suggest that they incorporate a small amount of Hf from fluid contaminated by subducted sediments. The rodingites are significantly enriched in Sr and depleted in large ion lithophile elements (LILE) (Cs, Rb, Ba). The fluid during rodingitization is able to extracts LILEs from the protolith of rodingites and adds Sr to the protolith of rodingites. The high field strength elements (HFSE) (Zr, Th, U, Nb, Ta) concentrations in the rodingites are similar to those of MORB, thus indicate their relatively immobile nature during rodingitization.

The petro-chemical characteristics of the arc lower-crust, important for understanding continental growth, have been rarely obtained because of their scarcity at the surface of the Earth. To constrain the formation age of the arc lower-crust, U–Pb zircon dating was applied to mafic enclaves in tonalites of the Tanzawa Tonalitic Pluton (TTP), which is regarded as the exposed middle crust of the former Izu–Bonin–Mariana arc, using a laser ablation-inductively coupled plasma–mass spectrometer (LA-ICP-MS). The texture and shape of mafic enclaves indicate an injection of mafic magma into tonalitic magma at the mid-crustal level. While 44 zircon grains from a host tonalite show a narrow-age distribution with a mean age of 4.6 ± 0.2 Ma, 301 zircon grains from 9 mafic enclaves show wide-age distributions from ca. 5 to 43 Ma. This study is the first to reveal a U–Pb age older than previously reported for the rock materials that compose the TTP, now identified to be 18 Ma compared with an age range from 4 Ma to 9 Ma. Because there are no other components of the TTP yet identified to be older than 17 Ma, the zircons separated from the TTP in this study which dated to be 18–43 Ma are interpreted to be xenocrysts derived from the arc lower-crust beneath the TTP. The oldest zircon age obtained from the mafic enclaves indicates that the formation of the arc lower-crust beneath TTP took place before 42.9 ± 8.6 Ma, consistent with the history of the Izu–Bonin–Mariana arc. This is the first time that the formation age of the lower crust has been estimated using zircons from mafic enclaves. This study shows that the zircon U–Pb dating from mafic enclaves in granites can yield significant information about the age of the continental lower crust.

The Ediacaran and Cambrian periods were one of the most important periods for the evolution of life. The biodiversity drastically expanded in the period. However, the origins are still ambiguous because surface environmental changes through the time have not been well understood yet. We conducted in-situ analyses of the phosphorus contents of carbonate minerals with a laser ablation-inductively coupled plasma-mass spectrometer (LA-ICP-MS) to estimate the phosphorus contents of seawater from the Ediacaran to the early Cambrian. Carbonate rocks contain not only the carbonate minerals but also detrital and authigenic materials such as silicate and phosphate minerals. Therefore, the whole rock compositions of carbonate rocks are not directly related with seawater composition. To avoid the influence of the involvement of the phosphate minerals, we performed the microscopic observation, elemental mapping of Si, Ca, Mg, Fe, and P contents with an electron probe microanalyzer (EPMA), and investigation of time profiles of signal intensities of Ca, Sr, Mn, P, La and Ba with the LA-ICP-MS. Especially, samples with low Mn/Sr ratios and primary textures such as oolites are suitable to estimate the primary phosphorus contents of the carbonates. The chemostratigraphy of the phosphorus contents of carbonates from the drill core and outcrop samples displays that the phosphorus contents decrease from ca. 400 ppm in the Ediacaran through ca. 200 ppm around the terminal Ediacaran and the beginning of the Cambrian to ca. 50 ppm in the early Cambrian. Previous works on 87Sr/86Sr chemostratigraphy from the Ediacaran to the Cambrian sections suggested relatively high continental influx in the middle Ediacaran, and around the Precambrian–Cambrian (PC/C) boundary. The high phosphorus content in the Ediacaran was possibly due to the high continental flux. On the other hand, previous works on chemostratigraphy of carbon isotope values of carbonate carbon from the Ediacaran to the Cambrian sections showed some large negative anomalies in the Ediacaran and around the Precambrian–Cambrian (PC/C) boundary, and suggested that the negative anomalies were caused by remineralization and respiration of dissolved organic matter. The degradation of the organic matter also accounts for the high phosphorus contents in the Ediacaran. The high phosphorus content of seawater favors enhancement of primary productivity and formation of phosphorites. The high phosphorus contents in the seawater possibly led to the emergence of the large, and motile organism through the enhancement of primary productivity and the consequent increase of oxygen content of the seawater.

We have conducted geochemical and mineralogical investigations of the rare earth and yttrium (REY)-rich mud from the Minami-Torishima area in the Pacific in order to clarify the concentration of REY and their host-phase in the mud. X-ray diffraction analysis shows that the mud is mainly composed of phillipsite, fluorapatite, quartz, albite, illite and montmorillonite. Whole-rock CaO, P2O5 and total REY contents of the mud are positively correlated. Relative abundance of apatite is also positively correlated to P2O5 and total REY contents. These correlations suggest that apatite is the main host of the P2O5 and REY in the mud. We make in situ compositional analyses of constituent minerals in the REY mud. The results show that the apatite is abundant in REY (9300–32,000 ppm) and is characterized by a negative Ce anomaly and enrichment in heavy rare-earth elements. This abundance and composition of REY of the mud is similar those of fish debris apatites. In contrast, phillipsite is less abundant in REY (60–170 ppm). Therefore we conclude that the main REY host phase of the mud is apatite.

We have investigated the petrography, geochemistry, and detrital zircon U–Pb LA-ICPMS dating of sandstone from the Gorkhi Formation of the Khangai–Khentei belt in the Ulaanbaatar area, central Mongolia. These data are used to constrain the provenance and source rock composition of the accretionary complex, which is linked to subduction of the Paleo-Asian Ocean within the Central Asian Orogenic Belt during the Middle Devonian to Early Carboniferous. Field and microscopic observations of the modal composition of sandstone and constituent mineral chemistry indicate that the sandstone of the Gorkhi Formation is feldspathic arenite, enriched in saussuritized plagioclase. Geochemical data show that most of the sandstone and shale were derived from a continental margin to continental island arc setting, with plutonic rocks being the source rocks. Detrital zircon 206 Pb/ 238 U ages of two sandstones yields age peaks of 322 ± 3 and 346 ± 3 Ma. The zircon 206 Pb/ 238 U age of a quartz–pumpellyite vein that cuts sandstone has a weighted mean age of 339 ± 3 Ma. Based on these zircon ages, we infer that the depositional age of sandstone within the Gorkhi Formation ranges from 320 to 340 Ma (i.e., Early Carboniferous). The provenance and depositional age of the Gorkhi Formation suggest that the evolution of the accretionary complex was influenced by the intrusion and erosion of plutonic rocks during the Early Carboniferous. We also suggest that spatial and temporal changes in the provenance of the accretionary complex in the Khangai–Khentei belt, which developed aound the southern continental margin of the Siberian Craton in relation to island arc activity, were influenced by northward subduction of the Paleo-Asian Ocean plate.

We have measured the U–Pb age of zircon grains separated from podiform chromitites from the Luobusa ophiolite, Southern Tibet, using laser ablation microprobe – inductively coupled plasma mass spectrometer (LA-IC-PMS), to determine the age relationship between the podiform chromitites and the host mantle peridotite. Spot analyses with LA-IC-PMS, assisted by cathodoluminescence images gave a wide age range, from the Cretaceous to the Late Archean (ca 100–2700 Ma). The minimum ages of ca 100 Ma, plotted on the concordia curve, were slightly lower than the metasomatic (magmatic) event in the supra-subduction zone (120 ± 10 Ma), suggesting that the zircons suffered some Pb loss. However, most of the ages found are much older than those of the chromitite and ophiolite formation. Laser Raman spectroscopy analyses revealed that the zircons recovered from the chromitites contain crustal mineral inclusions, such as quartz and K-feldspar, but lack mantle minerals (e.g., olivine, pyroxene, and chromite), suggesting that they had a crustal origin. The results indicate that crustal zircons in chromitites had a xenocrystic origin and resided in the mantle peridotite for a long period before being entrained into the chromitite during its formation. This indicates that the mantle peridotite under the Neo-Tethys Ocean was affected by the crustal material contamination. Our results are consistent with previous reports that mid-oceanic ridge basalts in the Indian Ocean have the isotopic signature of crustal material contamination. From these results, and previous isotopic studies on Gondwana geology, we conclude that ancient zircons from podiform chromitites could provide evidence of crustal material being recycled through the upper mantle.

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.

The two drill holes, which penetrated sub-horizontal rare earth element (REE) ore units at the Nechalacho REE in the Proterozoic Thor Lake syenite, Canada, were studied in order to clarify the enrichment mechanism of the high-field-strength elements (HFSE: Zr, Nb and REE). The REE ore units occur in the albitized and potassic altered miaskitic syenite. Zircon is the most common REE mineral in the REE ore units, and is divided into five types as follows: Type-1 zircon occurs as discrete grains in phlogopite, and has a chemical character similar to igneous zircon. Type-2 zircon consists of a porous HREE-rich core and LREE–Nb–F-rich rim. Enrichment of F in the rim of type-2 zircon suggests that F was related to the enrichment of HFSE. The core of type-2 zircon is regarded to be magmatic and the rim to be hydrothermal in origin. Type-3 zircon is characterized by euhedral to anhedral crystals, which occur in a complex intergrowth with REE fluorocarbonates. Type-3 zircon has high REE, Nb and F contents. Type-4 zircon consists of porous-core and -rim, but their chemical compositions are similar to each other. This zircon is a subhedral crystal rimmed by fergusonite. Type-5 zircon is characterized by smaller, porous and subhedral to anhedral crystals. The interstices between small zircon grains are filled by fergusonite. Type-4 and type-5 zircon grains have low REE, Nb and F contents. Type-1 zircon is only included in one unit, which is less hydrothermally altered and mineralized. Type-2 and type-3 zircon grains mainly occur in the shallow units, while those of type-4 and type-5 are found in the deep units. The deep units have high HFSE contents and strongly altered mineral textures (type-4 and type-5) compared to the shallow units. Occurrences of these five types of zircon are different according to the depth and degree of the hydrothermal alteration by solutions rich in F and CO3, which permit a model for the evolution of the zircon crystallization in the Nechalacho REE deposit as follows: (i) type-1 (discrete magmatic zircon) is formed in miaskitic syenite. (ii) LREE–Nb–F-rich hydrothermal zircon formed around HREE-rich magmatic zircon (type-2). (iii) type-3 zircon crystallized through the F and CO3-rich hydrothermal alteration of type-2 zircon which formed the complex intergrowth with REE fluorocarbonates; (iv) the CO3-rich hydrothermal fluid corroded type-3, forming REE–Nb-poor zircon (type-4). Niobium and REE were no longer stable in the zircon structure and crystallized as fergusonite around the REE–Nb-leached zircon (type-4); (v) type-5 zircon is formed by the more CO3-rich hydrothermal alteration of type-4 zircon, suggested by the fact that type-4 and type-5 zircon grains are often included in ankerite. Type-3 to type-5 zircon grains at the Nechalacho REE deposit were continuously formed by leaching and/or dissolution of type-2 zircon in the presence of F- and/or CO3-rich hydrothermal fluid. These mineral associations indicate that three representative hydrothermal stages were present and related to HFSE enrichment in the Nechalacho REE deposit: (i) F-rich hydrothermal stage caused the crystallization of REE–Nb-rich zircon (type-2 rim and type-3), with abundant formation of phlogopite and fluorite; (ii) F- and CO3-rich hydrothermal stage led to the replacement of a part of REE–Nb–F-rich zircon by REE fluorocarbonate; and (iii) CO3-rich hydrothermal stage resulted in crystallization of the REE–Nb–F-poor zircon and fergusonite, with ankerite. REE and Nb in hydrothermal fluid at the Nechalacho REE deposit were finally concentrated into fergusonite by way of REE–Nb–F-rich zircon in the hydrothermally altered units.

Taiwan formed during the Plio-Pleistocene collision of Eurasia with the outboard Luzon arc. Its pre-Tertiary basement, the Tananao metamorphic complex, consists of the western Tailuko belt and the eastern Yuli belt. These circum-Pacific belts have been correlated with the high-temperature/low-pressure (HT/LP) Ryoke belt and the high-pressure/low-temperature (HP/LT) Sanbagawa belt of Japan, respectively. To test this correlation and to reveal the architecture and plate-tectonic history of the Tananao metamorphic basement, detrital zircons were separated from 7 metasedimentary rock samples for U–Pb dating by LA-ICPMS techniques. Results of the present study, coupled with previous data, show that (1) the Tailuko belt consists of a Late Jurassic to earliest Cretaceous accretionary complex sutured against a Permian–Early Jurassic marble ± metabasaltic terrane, invaded in the north by scattered Late Cretaceous granitic plutons; the latter as well as minor Upper Cretaceous cover strata probably formed in a circum-Pacific forearc; (2) the Yuli belt is a mid- to Late Cretaceous accretionary complex containing HP thrust sheets that were emplaced attending the Late Cenozoic Eurasian plate–Luzon arc collision; (3) these two Late Mesozoic belts are not coeval, and in part were overprinted by low-grade metamorphism during the Plio-Pleistocene collision; (4) accreted clastic sediments of the Tailuko belt contain mainly Phanerozoic detrital zircons, indicating that terrigenous sediments were mainly sourced from western Cathaysia, whereas in contrast, clastic rocks of the Yuli accretionary complex contain a significant amount of Paleoproterozoic and distinctive Neoproterozoic zircons, probably derived from the North China craton and the Yangtze block ± eastern Cathaysia, as a result of continent uplift/exhumation after the Permo-Triassic South China–North China collision; and (5) the Late Jurassic–Late Cretaceous formation of the Tananao basement complex precludes the possibility that the early Yanshanian (Early Jurassic) granitoids in southern China represent a landward arc contemporaneous with the later, outboard Tananao accretionary event.

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.

We have developed a new calibration technique for multielement determination and U-Pb dating of zircon samples using laser ablation-inductively coupled plasma mass spectrometry (ICPMS) coupled with galvanometric optics. With the galvanometric optics, laser ablation of two or more sample materials could be achieved in very short time intervals (~10 ms). The resulting sample aerosols released from different ablation pits or different solid samples were mixed and homogenized within the sample cell and then transported into the ICP ion source. Multiple spot laser ablation enables spiking of analytes or internal standard elements directly into the solid samples, and therefore the standard addition calibration method can be applied for the determination of trace elements in solid samples. In this study, we have measured the rare earth element (REE) abundances of two zircon samples (Nancy 91500 and Prešovice) based on the standard addition technique, using a direct spiking of analytes through a multispot laser ablation of the glass standard material (NIST SRM612). The resulting REE abundance data show good agreement with previously reported values within analytical uncertainties achieved in this study (10% for most elements). Our experiments demonstrated that nonspectroscopic interferences on 14 REEs could be significantly reduced by the standard addition technique employed here. Another advantage of galvanometric devices is the accumulation of sample aerosol released from multiple spots. In this study we have measured the U-Pb age of a zircon sample (LMR) using an accumulation of sample aerosols released from 10 separate ablation pits of low diameters (~8 μm). The resulting (238)U-(206)Pb age data for the LMR zircons was 369 ± 64 Ma, which is in good agreement with previously reported age data (367.6 ± 1.5 Ma). (1) The data obtained here clearly demonstrate that the multiple spot laser ablation-ICPMS technique can become a powerful approach for elemental and isotopic ratio measurements in solid materials.

Geochemical and mineralogical studies were conducted on the 12-m-thick weathering profile of the Kata Beach granite in Phuket, Thailand, in order to reveal the transport and adsorption of rare earth elements (REE) related to the ion-adsorption type mineralization. The parent rock is ilmenite-series biotite granite with transitional characteristics from I type to S type, abundant in REE (592 ppm). REE are contained dominantly in fluorocarbonate as well as in allanite, titanite, apatite, and zircon. The chondrite-normalized REE pattern of the parent granite indicates enrichment of LREE relative to HREE and no significant Ce anomaly. The upper part of the weathering profile from the surface to 4.5 m depth is mostly characterized by positive Ce anomaly, showing lower REE contents ranging from 174 to 548 ppm and lower percentages of adsorbed REE from 34% to 68% compared with the parent granite. In contrast, the lower part of the profile from 4.5 to 12 m depth is characterized by negative Ce anomaly, showing higher REE contents ranging from 578 to 1,084 ppm and higher percentages from 53% to 85%. The negative Ce anomaly and enrichment of REE in the lower part of the profile suggest that acidic soil water in an oxidizing condition in the upper part mostly immobilized Ce4+ as CeO2 and transported REE3+ downward to the lower part of the profile. The transported REE3+ were adsorbed onto weathering products or distributed to secondary minerals such as rhabdophane. The immobilization of REE results from the increase of pH due to the contact with higher pH groundwater. Since the majority of REE in the weathered granite are present in the ion-adsorption fraction with negative Ce anomaly, the percentages of adsorbed REE are positively correlated with the whole-rock negative Ce anomaly. The result of this study suggests that the ion-adsorption type REE mineralization is identified by the occurrence of easily soluble REE fluorocarbonate and whole-rock negative Ce anomaly of weathered granite. Although fractionation of REE in weathered granite is controlled by the occurrence of REE-bearing minerals and adsorption by weathering products, the ion-adsorption fraction tends to be enriched in LREE relative to weathered granite.

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

We report results from U–Pb analyses by laser ablation ICP mass spectrometry of zircons in ultrahigh-temperature garnet-cordierite gneisses and A-type granite intrusions within the Achankovil Shear/Suture Zone in southern India, a region considered to mark the zone of the latest Neoproterozoic-Cambrian Gondwana collision. Field evidence and geochronologic data for the gneisses and granites suggests the possibility for the multi-heating of metamorphism in earlier stage and magmatism in later stage. Zircon U–Pb dating for 138 spots on 123 grains yielded well-defined age peaks at 480–560 Ma and less prominent age peaks at approximately 600–900 Ma in compiled age data histograms. The Neoproterozoic ages of ca. 600–900 Ma correlating with the protolith history might suggest the magmatic and metamorphic processes in a subduction-accretion regime prior to the final collision during latest Neoproterozoic-Cambrian. The ages of 480–560 Ma obtained from the granites correlate with the final suturing of the Gondwana supercontinent.