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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.

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.

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.

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 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.

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 redox state of Precambrian shallow seas has been linked with material cycle and evolution of the photosynthesis-based ecosystem. Iron is a redox-sensitive element and exists as a soluble Fe(II) species or insoluble Fe(III) species on Earth’s surface. Previous studies have shown that the iron isotopic ratio of marine sedimentary minerals is useful for understanding the ocean redox state, although the redox state of the Archean shallow sea is poorly known. This is partly because the conventional bulk isotope analytical technique has often been used, wherein the iron isotopic record may be dampened by the presence of isotopically different iron-bearing minerals within the same sample. Here we report a microscale iron isotopic ratio of individual pyrite grains in shallow marine stromatolitic carbonates over geological time using a newly developed, near-infrared femtosecond laser ablation multicollector ICP-MS technique (NIR-fs-LA-MC-ICP-MS). We have determined that the grain-scale iron isotopic distribution of pyrite from coeval samples shows a bimodal (2.7 and 2.3 Ga) or unimodal pattern (2.9, 2.6, and 0.7 Ga). In particular, pyrite from the 2.7 Ga Fortescue Group shows a unique bimodal distribution with highly positive (+1.0‰ defined as Type 1) and negative δ56Fe values (−1.8‰ defined as Type 2). Type 1 and 2 pyrites occasionally occur within different siliceous layers in the same rock specimen. Layer-scale iron isotopic heterogeneity indicates that the iron isotopic ratios of the two types of pyrite are not homogenized by diagenesis after deposition. Some cubic pyrites have a core with a positive δ56Fe value (1‰) and a rim with a crustal δ56Fe value (0‰). The observed isotopic zoning suggests that the positive δ56Fe value is a primary signature at the time of stromatolite formation, while secondary pyrite precipitated during diagenesis. The positive δ56Fe value of Type 1 and the large iron isotopic difference between Type 1 and 2 (2.8‰.) suggest partial Fe(II) oxidation in the 2.7-Ga shallow sea, i.e., pyritization of 56Fe-enriched ferric oxyhydroxide (Type 1) and 56Fe depleted Fe2+aq in seawater (Type 2). Type 2 pyrite was probably not produced by microbial iron redox cycling during diagenesis because this scenario requires a higher abundance of pyrite with δ56Fe of 0‰ than of −1.8‰. Consequently, the degree of Fe(II) oxidation in the 2.7-Ga shallow sea can be estimated by a Fe2+aq steady-state model. The model calculation shows that half the Fe2+aq influx was oxidized in the seawater. This implies that O2 produced by photosynthesis would have been completely consumed by oxidation of the Fe2+aq influx. Grain-scale iron isotopic distribution of pyrite could be a useful index for reconstructing the redox state of the Archean shallow sea.

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.

The Palghat–Cauvery suture zone in southern India separates Archaean crustal blocks to the north and the Proterozoic Madurai block to the south. Here we present the first detailed study of a partially retrogressed eclogite (from within the Sittampundi anorthositic complex in the suture zone) that occurs as a 20-cm wide layer in a garnet gabbro layer in anorthosite. The eclogite largely consists of an assemblage of coexisting porphyroblasts of almandine–pyrope garnet and augitic clinopyroxene. However, a few garnets contain inclusions of omphacite. Rims and symplectites composed of Na–Ca amphibole and plagioclase form a retrograde assemblage. Petrographic analysis and calculated phase equilibria indicate that garnet–omphacite–rutile–melt was the peak metamorphic assemblage and that it formed at ca . 20 kbar and above 1000 °C. The eclogite was exhumed on a very tight hairpin-type, anticlockwise P–T path, which we relate to subduction and exhumation in the Palghat–Cauvery suture zone. The REE composition of the minerals suggests a basaltic oceanic crustal protolith metamorphosed in a subduction regime. Geological–structural relations combined with geophysical data from the Palghat–Cauvery suture zone suggest that the eclogite facies metamorphism was related to formation of the suture zone. Closure of the Mozambique Ocean led to development of the suture zone and to its western extension in the Betsimisaraka suture of Madagascar.

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.

The tectonic evolution of the Northern Shimanto belt, central Shikoku, Japan, was examined based on petrological and geochronological studies in the Oboke area, where mafic schists of the Kawaguchi Formation contain sodic amphibole (magnesioriebeckite). The peak P–T conditions of metamorphism are estimated as 4–4.5 kbar (15–17 km depth), and 240–270 °C based on available phase equilibria and sodic amphibole compositions. These metamorphic conditions are transitional between blueschist, greenschist and pumpellyite–actinolite facies. Phengite K–Ar ages of 64.8 ± 1.4 and 64.4 ± 1.4 Ma were determined for the mafic schists, and 65.0 ± 1.4, 61.4 ± 1.3 and 63.6 ± 1.4 Ma for the pelitic schists. The metamorphic temperatures in the Oboke area are below the closure temperature of the K–Ar phengite system, so the K–Ar ages date the metamorphic peak in the Northern Shimanto belt. In the broad sense of the definition of blueschist facies, the highest-grade part of the Northern Shimanto belt belongs to the blueschist facies. Our study and those of others identify the following constraints on the possible mechanism that led to the exhumation of the overlying Sanbagawa belt: (i) the Sanbagawa belt is a thin tectonic slice with a structural thickness of 3–4 km; (ii) within the belt, metamorphic conditions varied from 5 to 25 kbar, and 300 to 800 °C, with the grade of metamorphism decreasing symmetrically upward and downward from a structurally intermediate position; and (iii) the Sanbagawa metamorphic rocks were exhumed from ∼60 km depth and emplaced onto the Northern Shimanto metamorphic rocks at 15–17 km depth and 240–270 °C. Integration of these results with those of previous geological studies for the Sanbagawa belt suggests that the most probable exhumation mechanism is wedge extrusion.

We estimated metamorphic conditions for the ~ 6 Ma Taitao ophiolite, associated with the Chile triple junction. The metamorphic grade of the ophiolite, estimated from secondary matrix minerals, changes stratigraphically downwards from the zeolite facies, through the prehnite-actinolite facies, greenschist facies and the greenschist-amphibolite transition, to the amphibolite facies. The metamorphic facies series corresponds to the low-pressure type. The metamorphic zone boundaries are subparallel to the internal lithological boundaries of the ophiolite, indicating that the metamorphism was due to axial hydrothermal alteration at a mid-ocean ridge. Mineral assemblages and the compositions of veins systematically change from quartz-dominated, through epidote-dominated, to prehnite-dominated with increasing depth. Temperatures estimated from the vein assemblages range from ~ 230 [degree sign]C in the volcanic unit to ~ 380 [degree sign]C at the bottom of the gabbro unit, systematically ~ 200 [degree sign]C lower than estimates from the adjoining matrix minerals. The late development of veins and the systematically lower temperatures suggest that the vein-forming alteration was due to off-axis hydrothermal alteration. Comparison between the Taitao ophiolite with its mid-ocean ridge (MOR) affinity, and other ophiolites and MOR crusts, suggests that the Taitao ophiolite has many hydrothermal alteration features similar to those of MOR crusts. This is consistent with the tectonic history that the Taitao ophiolite was formed at the South Chile ridge system near the South American continent (Anma, R., Armstrong, R., Danhara, T., Orihashi, Y. and Iwano, H., 2006. Zircon sensitive high mass-resolution ion microprobe U-Pb and fission-track ages for gabbros and sheeted dykes of the Taitao ophiolite, Southern Chile, and their tectonic implications. The Island Arc, 15(1): 130-142).

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.