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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.

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.

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.

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.

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.

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.

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.

The paper presents LA ICP MS U–Pb age data on detrital zircons from sands of major Russian rivers: the Don, Volga, Ob’, Yenisey and Amur. The obtained data are discussed in terms of major episodes of granitic magmatism, which are recorded in the continental blocks that form the modern Eurasian continent. Results are compared with published igneous and detrital zircon age data obtained from parental and sedimentary rocks of the river basins under consideration and worldwide. The U–Pb age results allowed us to confirm (i) the episodic character of continent formation; (ii) the Neoarchean global magmatic event and, possibly, formation of the Kenorland supercontinent; (iii) the global episode of crust formation at 2.0–1.8 Ga, which formed the Columbia supercontinent; (iv) the breakup of Columbia at 1.3–1.2 Ga; (v) the major period of Phanerozoic crustal growth in Central Asia which is likely to be a result of the Altaid orogeny. On the other hand, our data did not unambiguously confirm previous idea about the global character of the Grenvillian and Pan-African orogenies as a result of the assembly of Rodinia and Gondwana, respectively. The “Rodinia” peak is not observed in the histograms of the Ob’, Yenisey and Amur, whereas the “Gondwana” signature is not obvious in the histograms of the Don, Volga and Amur. Of special interest are the 2.7–2.5 Ga and 2.0–1.7 Ga peaks in the Ob’ zircon age spectrum in spite of the absence of so far identified Archean and Paleoproterozoic parental rocks in the Ob’ catchment area. The obtained age spectra were joined into three groups based on statistics: Baltica (Don and Volga), Siberia (Ob’ and Yenisey) and East Asia (Amur). For future reconstructions we suggest to include all the available results on Don and Volga rivers into a North America-Baltica Group corresponding to Laurentia-derived continental blocks, and to consider a Siberia Group (Siberian Craton; Ob’, Yenisey, Lena, Indigirka rivers) and an East Asia Group (North and South China cratonic blocks; Amur, Yellow, Yangtze and Mekong rivers).

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.

To constrain the timing of the tectonothermal events and formation process of a plutonic suite, U–Pb dating was carried out by laser ablation inductively coupled plasma mass spectrometry combined with cathodoluminescence imaging on zircon grains extracted from the Bato pluton, northern Yamizo Mountains, Japan. The Bato pluton consists of gabbro and diorite. Zircon grains separated from a gabbro sample had a unimodal 238U–206Pb age (105.7 ±1.0 Ma). It was interpreted as the solidification age of the gabbro. Cathodoluminescence observation showed that the zircon grains from a diorite sample were characterized by anhedral cores, oscillatory zoned mantles, and dark rims. The 238U–206Pb age of the anhedral cores ranged from 2 165 Ma to 161 Ma, indicating the assimilation of surrounding sedimentary rocks. The 238U–206Pb ages of the oscillatory zoned mantles and dark rims are 109.0 ±1.3 Ma and 107.7 ±1.3 Ma, respectively. Observation under polarizing microscopy suggests that the anhedral cores occurred before plagioclase and hornblende, and the oscillatory zones around the anhedral cores had crystallized at the same time as the crystallization of biotite. Moreover, the dark rims formed at the same time as the crystallization of quartz and K-feldspar. The formation process of the gabbro-diorite complex in the Bato pluton was inferred as follows. (i) A mafic initial magma intruded into Mesozoic sedimentary rocks, and the assimilation of these sedimentary rocks led to geochemical variation yielding a dioritic composition. Subsequently, plagioclase and hornblende of the diorite were crystallized before 109.0 ±1.3 Ma. (ii) Biotite crystallized in the middle stage around 109.0 ±1.3 Ma. (iii) Quartz and K-feldspar of the diorite were crystallized at 107.7 ±1.3 Ma. The gabbroic magma solidified (105.7 ±1.0 Ma) after solidification of the diorite.