Microscale Simultaneous Measurement of Carbon and Nitrogen Isotopes on Natural Diamond

Simultaneous analysis of carbon and nitrogen isotope ratios by SIMS was applied for the first-time to a natural diamond from the Kelsey Lake kimberlite, State Line Distinct, Colorado (UWD-1). This in situ procedure is faster, reduces sample size for analysis, and measures both isotope ratios from a single ~ 10 μm diameter pit, a critical advantage for zoned diamonds. The carbon isotope ratio (expressed as δ¹³C_VPDB) of the bulk UWD-1 crystal, determined by the conventional combustion method in the present study, is -5.9‰ ± 0.2‰ (VPDB, 2s). Nitrogen mass fraction ([N]) and isotope ratio (expressed as δ¹⁵N_Air) were determined by stepwise combustion and gas-source mass-spectrometry, resulting in 553 ± 64 μg g^-1 and -6.7‰ ± 1.1‰ (Air, 2s), respectively. Secondary ions of ¹²C₂^-, ¹²C¹³C^-, ¹²C¹⁴N^-, and ¹²C¹⁵N^- were simultaneously measured by SIMS using three Faraday cups and one electron multiplier. The spot-to-spot reproducibility of δ¹³C and δ¹⁵N values for the UWD-1 (178 spots on sixteen chips, 10 μm spots), were 0.3‰ and 1.6‰, respectively (2s). While ¹²C¹⁴N^-/¹²C₂^- ratios, which are an indicator for [N], varied up to 12% among these sixteen chips, such variation did not correlate with either δ¹³C or δ¹⁵N values. We propose that UWD-1 is a suitable reference sample for microscale in situ analysis of δ¹³C and δ¹⁵N values in diamond samples.     

Calibration of oxygen isotope fractionation and calcite-corundum thermometry in emery at Naxos,Greece

Corundum (Crn), including sapphire, occurs in emery pods surrounded by marble on the island of Naxos, Greece. The emery formed from bauxite deposited in karst that was metamorphosed to 400–700°C at 20–15 Ma. Many of these rocks initially appeared well suited for refractory accessory mineral (RAM) thermometry, which uses oxygen isotope fractionation between a RAM – corundum – and a modally dominant phase with faster diffusion of oxygen – calcite (Cc) – to determine peak metamorphic temperatures. However, previous attempts at oxygen isotope thermometry were confounded by highly variable fractionations (Δ¹⁸O) measured at mm-scale and the uncertain calibration of Δ¹⁸O(Cc-Crn) versus temperature. Secondary ion mass spectrometry (SIMS) permits in situ analysis of δ¹⁸O in corundum and calcite at the 10-μm scale in adjacent grains where textures suggest peak metamorphic equilibrium was attained. SIMS analyses of adjacent mineral pairs in eight rocks yield values of Δ(Cc-Crn) that systematically decrease from 7.2 to 2.9‰ at higher metamorphic grade. Pairing these data with independent temperature estimates from mineral isograds yields an empirical calibration of 1,000 lnα(Cc-Crn) = 2.72 ± 0.3 × 10⁶/T² (T in K). The new fractionations (2.7‰ at 1,000 K) are significantly smaller than those calculated from the modified increment method (6.5‰ at 1,000 K; Zheng, Geochimica et Cosmochimica Acta, 1991, 55:2299–2307; Zheng, Mineral Mag, 1994, 58A:1000–1001), which yield unreasonably high temperatures of 630 to 1,140°C when applied to the new Naxos data. The new calibration of Δ(Cc-Crn) can be combined with published fractionations to calculate A-factors for corundum versus a range of 14 other minerals. These new fractionation factors can be used for thermometry or to constrain the genesis of corundum. A compilation of gem corundum δ¹⁸O values shows that many igneous sapphires, including important deposits of basalt-associated sapphire, are mildly elevated in δ¹⁸O relative to the calculated range in equilibrium with mantle values (4.4–5.7‰) and formed from evolved magmas.     

Secondary Ion Mass Spectrometry Bias on Isotope Ratios in Dolomite–Ankerite,Part II: δ13C Matrix Effects

This study is Part II of a series that documents the development of a suite of calibration reference materials for in situ SIMS analysis of stable isotope ratios in Ca‐Mg‐Fe carbonates. Part I explored the effects of Fe²⁺ substitution on SIMS δ¹⁸O bias measured from the dolomite–ankerite solid solution series [CaMg(CO₃)₂–CaFe(CO₃)₂], whereas this complementary work explores the compositional dependence of SIMS δ¹³C bias (calibrated range: Fe# = 0.004–0.789, where Fe# = molar Fe/(Mg+Fe)). Under routine operating conditions for carbonate δ¹³C analysis at WiscSIMS (CAMECA IMS 1280), the magnitude of instrumental bias increased exponentially by 2.5–5.5‰ (session‐specific) with increasing Fe‐content in the dolomite structure, but appeared insensitive to minor Mn substitution [< 2.6 mole % Mn/(Ca+Mg+Fe+Mn)]. The compositional dependence of bias (i.e., the matrix effect) was expressed using the Hill equation, yielding calibration residual values ≤ 0.3‰ relative to CRM NBS‐19 for eleven carbonate reference materials (6‐μm‐diameter spot size measurements). Based on the spot‐to‐spot repeatability of a drift monitor material that ‘bracketed’ each set of ten sample‐spot analyses, the analytical precision was ± 0.6–1.2‰ (2s, standard deviations). The analytical uncertainty for individual sample analyses was approximated by combining the precision and calibration residual values (propagated in quadrature), suggesting an uncertainty of ± 1.0–1.5‰ (2s).     

Characteristics of the ratio of dissolved cadmium to phosphate in subtropical coastal waters of Ishigaki Island,Okinawa, Japan

The ratio of dissolved cadmium (Cd) to phosphate (PO₄) in the subtropical coastal area of Ishigaki Island, Okinawa, Japan, was investigated. Twenty vertical seawater samplings were carried out once a month from May 2008 to January 2010. In order to examine how the Cd/PO₄ ratio in seawater varies with the oceanographic conditions (i.e., the water temperature–salinity characteristics), the water masses at the study sites were classified into two types: group 1 with a water temperature of >25°C and a salinity range of 34.0–34.4, and group 2 with a water temperature of <25°C and a salinity of >34.4. A different phytoplankton assemblage was observed in each water mass defined. Different Cd/PO₄ ratios were obtained for the two water mass types, due to the differences between the types in terms of the environmental conditions such as the water temperature–salinity (T–S) characteristics and phytoplankton assemblages, as well as possible variations in the concentrations of dissolved iron, zinc, manganese, and CO₂ in seawater in each water mass.     

Eclogite-facies fluid infiltration: constraints from δ18O zoning in garnet

In situ analysis reveals that eclogite-facies garnets are zoned in δ¹⁸O with lower values in the core and rims that are ~1.5 to 2.5 ‰ higher. This pattern is present in 9 out of 12 garnets analyzed by SIMS from four orogenic eclogite terranes, and correlates with an increase in the mole fraction of pyrope and Mg/Fe ratio from core to rim, indicating prograde garnet growth. At the maximum temperatures and the time-scales experienced by these garnets, calculated intragranular diffusion distances for oxygen are small (<5 μm), indicating that δ¹⁸O records primary growth zoning and not diffusive exchange. The oxygen isotope gradients are larger than could form due to temperature changes during closed-system mineral growth. Thus, gradients reflect the compositions of fluids infiltrating during prograde metamorphism. Values of δ¹⁸O in garnet cores range from ?1 to 15 ‰, likely preserving the composition of the eclogite protoliths. Two garnet cores from the Almenningen eclogite in the Western Gneiss Region, Norway, have δ¹⁸O ~?1 ‰ and are the first negative δ¹⁸O eclogites identified in the region. In contrast with orogenic eclogites, seven high δ¹⁸O garnets (>5 ‰) from two kimberlites are homogeneous in δ¹⁸O, possibly due to diffusive exchange, which is possible for prolonged periods at higher mantle temperatures. Homogeneity of δ¹⁸O in garnets outside the normal mantle range (5–6 ‰) may be common in kimberlitic samples.     

Silicification of pelitic schist in the Ryoke low-pressure/temperature metamorphic belt, Southwest Japan: Origin of competent layers in the middle crust

We propose that competent layers composed of silicified rocks in the Cretaceous Ryoke low-pressure/temperature (low- P/T ) metamorphic belt in the Iwakuni–Yanai area, Southwest Japan, may be an exhumed equivalent of a seismically-reflective bright-layer in the middle crust. Silicified rocks crop out as layers or long lenticular bodies several to fifteen meters in thickness, and they are restricted to the area of greenschist facies conditions within a structural thickness of about one kilometer. The silicified rock layers exhibit a sharp contact with subjacent biotite schist but a gradational contact with overlying pelitic schist. Silicified rock is mainly composed of fine-grained quartz and minor muscovite and biotite, and some colored minerals have been variably decolorized by alteration. This implies that silicification turned the color of pelitic schists to pale gray or milky white. Quartz veins cutting schistosity at high angles were preferentially developed in the silicified rocks, while schistosity-parallel quartz veins, which underwent viscous flow, were observed in the underlying biotite schists. En echelon quartz veins and fishnet-like quartz veins are characteristic of silicified rocks. The modes of occurrence of quartz veins indicate that silicified rocks were competent relative to underlying biotite schist. The combination of contact with high-competence contrast adjacent to low-permeability silicified rocks may be a good reflector of seismic waves. If the silicified rocks were distributed in the middle crust to a considerable extent, they may result in seismic bright-layer reflections.     

U–Pb zircon geochronology of the North Pole Dome adamellite in the eastern Pilbara Craton

Supracrustal rocks around the North Pole Dome area, Western Australia, provide valuable information regarding early records of the evolution of crustal processes, surface environments, and biosphere. Owing to the occurrence of the oldest known microfossils, the successions at the North Pole Dome area have attracted interest from many researchers. The Paleoarchean successions (Warrawoona Group) mainly comprise mafic‐ultramafic greenstones with intercalated cherts and felsic lavas. Age constraints on the sediments have been mainly based on zircon U–Pb geochronology. However, many zircon grains have suffered from metamictization and contain anomalously high contents of common Pb, which makes interpretation of the U–Pb data complicated. In order to provide more convincing chronological constraints, an U–Pb Concordia age is widely accepted as the best estimate. Most zircons separated from two adamellites also suffered from severe metamictization. In our analyses, less metamictized domains were selected using a pre‐ablation technique in conjunction with elemental mapping, and then their U–Pb isotopic compositions were determined with a laser ablation inductively coupled plasma mass spectrometry. Most analyzed domains contained certain amounts of common Pb (²⁰⁴Pb/²⁰⁶Pb > 0.000 1), whereas three and five U–Pb data points with less common Pb (²⁰⁴Pb/²⁰⁶Pb < 0.000 1) were obtained. These U–Pb datasets yielded U–Pb Concordia ages of ca 3 445 Ma and 3 454 Ma, respectively. These ages represent the timing of the adamellite intrusion, and constrain the minimum depositional age of the Warrawoona Group. In addition, a single xenocrystic zircon grain showed a ²⁰⁷Pb/²⁰⁶Pb age of ca 3 545 Ma, supporting the idea that the sialic basement of the Pilbara Craton existed prior to 3 500 Ma. The in situ U–Pb zircon dating combined with the pre‐ablation technique has the potentials to identify non‐metamictized parts and to yield precise and accurate geochronological data even from partially metamictized zircons.