Abstract Background Monazite, a moderately common light rare earth element (LREE) and thorium phosphate mineral, has chemical, age, and isotopic characteristics that are useful in the investigation of the origin and evolution of crustal melts and fluid-rock interactions. Multiple stages of growth and partial recrystallization commonly observed in monazite inevitably require microspot chemical and isotopic analyses, for which well-characterized reference materials are essential to correct instrumental biases. In this study, we introduce new monazite reference materials COM-1 and Hongcheon for the use in the microspot analysis of oxygen isotopic composition. Findings COM-1 and Hongcheon were derived from a late Mesoproterozoic (~ 1080 Ma) pegmatite dyke in Colorado, USA, and a Late Triassic (~ 230 Ma) carbonatite-hosted REE ore in central Korea, respectively. The COM-1 monazite has much higher levels of Th (8.77 ± 0.56 wt.%), Si (0.82 ± 0.07 wt.%) and lower REE contents (total REE = 49.5 ± 1.2 wt.%) than does the Hongcheon monazite (Th, 0.23 ± 0.11 wt.%; Si, < 0.1 wt.%; total REE, 59.9 ± 0.7 wt.%). Their oxygen isotopic compositions (δ 18 O VSMOW ) were determined by gas-source mass spectrometry with laser fluorination (COM-1, 6.67 ± 0.08‰; Hongcheon-1, 6.60 ± 0.02‰; Hongcheon-2, 6.08 ± 0.07‰). Oxygen isotope measurements performed by a Cameca IMS1300-HR 3 ion probe showed a strong linear dependence ( R 2 = 0.99) of the instrumental mass fractionation on the total REE contents. Conclusions We characterized chemical and oxygen isotopic compositions of COM-1 and Hongcheon monazites. Their internal homogeneity in oxygen isotopic composition and chemical difference provide an efficient tool for calibrating instrumental mass fractionation occurring during secondary ion mass spectrometry analyses.
A trace element composition of rock samples is difficult to determine when they contain refractory minerals that are hardly dissolved with conventional acid digestion techniques. Fused glass beads of rock samples could be an adequate target to circumvent this problem. We here report inductively coupled plasma-mass spectrometry (ICP-MS) results for geological reference materials (GRMs) prepared to normal- (sample/flux = 1:5) and low-dilution (sample/flux = 1:2) glass beads by using Nd:YAG UV 213-nm laser ablation system. Concentrations of 24 trace elements (Ba, Hf, Nb, Rb, Sr, Ta, Th, U, Y, Zr, and 14 rare earth elements (REEs)) were analyzed for three USGS GRMs (G-3 granite, AGV-2 andesite, and BHVO-2 basalt). Each analysis for the GRM beads was performed as spot (ca. 55 μm diameter) analysis with 120-s ablation time. The depth-to-diameter ratio of the laser spot was low (<4) enough to prevent significant elemental fractionation. The NIST612 glass and 29Si were employed as the external standard and the internal standard element, respectively. When the middle half of time-integrated data was taken to minimize the fractionation effect, the low-dilution fused glasses yielded reproducible and accurate results for all analyzed elements. In the case of normal-dilution fused glasses, comparable precision and accuracy were obtained only for elements with concentrations higher than 1 μg g−1, likely resulting from higher dilution ratios. Low-dilution glass beads can be an adequate target to analyze trace element composition of rock samples by using the laser ablation ICP-MS. This simple and rapid technique can be applied directly to the same glass beads prepared for major elemental analysis using the XRF.
Northeast Asian continental margins contain the products of magma emplacement driven by prolonged subduction of the (paleo-)Pacific plate. As observed in many Cordilleran arcs, magmatic evolution in this area was punctuated by high-volume pulses amid background periods. The present study investigates the early evolution of the Cretaceous magmatic flare-up using new and published geochronological, geochemical, and O-Hf isotope data from plutonic rocks in the southern Korean Peninsula. After a long (∼50 m.y.) magmatic hiatus and the development of the Honam Shear Zone through flat-slab subduction, the Cretaceous flare-up began with the intrusion of monzonites, granodiorites, and granites in the inboard Gyeonggi Massif and the intervening Okcheon Belt. Compared to Jurassic granitoids formed during the former flare-up, Albian (∼111 Ma) monzonites found in the Eopyeong area of the Okcheon Belt have distinctly higher zircon εHf(t) (−7.5 ± 1.3) and δ18O (7.78‰ ± 0.25‰) values and lower whole-rock La/Yb and Sr/Y ratios. The voluminous coeval granodiorite and granite plutons in the Gyeonggi Massif are further reduced in Sr/Y and to a lesser extent, in La/Yb, and have higher zircon εHf(t) values (−13 to −19) than the Precambrian basement (ca. −30). These chemical and isotopic features indicate that Early Cretaceous lithospheric thinning, most likely resulting from delamination of tectonically and magmatically overthickened lithospheric keel that was metasomatized during prior subduction episodes, and consequent asthenospheric upwelling played vital roles in igniting the magmatic flare-up. The O-Hf isotopic ranges of synmagmatic zircons from the Albian plutons and their Paleoproterozoic and Jurassic inheritance attest to the involvement of lithospheric mantle and crustal basement in magma generation during this decratonization event. Arc magmatism then migrated trenchward and culminated in the Late Cretaceous, yielding widespread granitoid rocks emplaced at shallow crustal levels. The early Late Cretaceous (94–85 Ma) granites now prevalent in Seoraksan-Woraksan-Sokrisan National Parks are highly silicic and display flat chondrite-normalized rare earth element patterns with deep Eu anomalies. Synmagmatic zircons in these granites mimic their host rock's chemistry. Delamination-related rejuvenation of crustal protoliths is indicated by zircon εHf(t) values of granites (−6 to −20) that are consistently higher than the Precambrian basement value. Concomitant core-to-rim variation in zircon O-Hf isotopic compositions reflects a typical sequence of crustal assimilation and fresh input into the magma chamber.
This study introduces a new zircon reference material, LKZ-1, for the in situ U–Pb dating and O–Hf isotopic and trace element analyses. The secondary ion mass spectrometric analyses for this gem-quality single-crystal zircon yielded a weighted mean 206Pb/238U age of 572.6 ± 2.0 Ma (2σ, n = 22, MSWD = 0.90), with moderately high U concentrations (619 ± 21 ppm, 1 SD), restricted Th/U ratios (0.146 ± 0.002, 1 SD), and negligible common Pb content (206Pbc < 0.2%). A comparable 206Pb/238U age (570.0 ± 2.5 Ma, 2σ) was produced by the isotope dilution-thermal ionization mass spectrometry. The secondary ion mass spectrometric and laser ablation-assisted multiple collector inductively coupled plasma mass spectrometer analyses respectively showed that LKZ-1 had little variation in O (δ18OV-SMOW = 10.65 ± 0.14‰; laser fluorination value = 10.72 ± 0.02‰; 1 SD) and Hf (176Hf/177Hf = 0.281794 ± 0.000016, 1 SD) isotopic compositions. LKZ-1 was also fairly homogeneous in its chemical composition (RSD of laser ablation ICPMS data ≤ 10%), displaying a relatively uniform chondrite-normalized rare earth element pattern ((Lu/Gd)N = 31 ± 3, Eu/Eu* = 0.43 ± 0.17, Ce/Ce* = 44 ± 32; 1 SD). These consistencies suggest that the LKZ-1 zircon is a suitable working standard for geochronological and geochemical analyses.
Zircon oxygen-hafnium and biotite magnesium isotopic compositions of Late Cretaceous to Oligocene (88–27 Ma) granitoids from the Gyeongsang continental arc, southeastern Korea, collectively provide a new insight into shallow magma petrogenesis. Zircon crystals extracted from eight calc-alkaline or alkaline plutons commonly contain xenocrystic cores and typically show magmatic cathodoluminescence zonings and sharp Raman spectra. Most zircons have positive eHf values plotting below the mid-ocean-ridge basalt evolution path, indicating that the arc magmatism was dominated by the recycling of juvenile materials. Zircon δ18O values shifted upward or downward from the mantle range attest to the O isotopic exchange of protoliths with surface waters at various temperature conditions. Small (<1‰) but discernable core-to-rim decreases of δ18O values are recognized selectively in magmatic zircon grains from four plutons possessing biotite δ26Mg values (–0.07‰ to +2.32‰) distinctly higher than the mantle range. Such a concomitant O-Mg isotopic variation provides compelling evidence for a series of self-induced hydrothermal alteration and assimilation processes (i.e., crustal self-cannibalization). This study shows that the supracrustal input to magmas in a young and juvenile orogen can be traced effectively by the combination of stable isotope records from the plutonic root.
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