Plesovice zircon : A new natural reference material for U-Pb and Hf isotopic microanalysis

We present the first finding of continental crust-derived Precambrian zircons in garnet/spinel pyroxenite veins within mantle xenoliths carried by the Neogene Hannuoba basalt in the central zone of the North China Craton (NCC). Petrological and geochemical features indicate that these mantle-derived composite xenoliths were formed by silicic melt^lherzolite interaction. The Precambrian zircon ages can be classified into three age groups of 2·4^2·5 Ga, 1·6^2·2 Ga and 0·6^1·2 Ga, coinciding with major geological events in the NCC. These Precambrian zircons fall in the field of continental granitoid rocks in plots of U/Yb vs Hf and Y. Their igneous-type REE patterns and metamorphic zircon type CL images indicate that they were not crystallized during melt^peridotite interaction and subsequent high-pressure metamorphism.The 2·5 Ga zircons have positive eHf(t) values (2·9^10·6), whereas the younger Precambrian zircons are dominated by negative eHf(t) values, indicating an ancient continental crustal origin.These observations suggest that the Precambrian zircons were xenocrysts that survived melting of recycled continental crustal rocks and were then injected with silicate melt into the host peridotite. In addition to the Precambrian zircons, igneous zircons of 315 3 Ma (2 ), 80^170 Ma and 48^64 Ma were separated from the garnet/spinel pyroxenite veins; these provide evidence for lower continental crust and oceanic crust recycling-induced multi-episodic melt^peridotite interactions in the central zone of the NCC. The combination of the positive eHf(t) values (2·91^24·6) of the 315 Ma zircons with the rare occurrence of 302^324 Ma subduction-related diorite^granite plutons in the northern margin of the NCC implies that the 315 Ma igneous zircons might record melt^peridotite interactions in the lithospheric mantle induced by Palaeo-Asian oceanic crust subduction. Igneous zircons of age 80^170 Ma generally coexist with the Precambrian metamorphic zircons and have lower Ce/Yb and Th/U ratios, higher U/Yb ratios and greater negative Eu anomalies.The eHf(t) values of these zircons vary greatly from ^47·6 to 24·6.The 170^110 Ma zircons are generally characterized by negative eHf(t) values, whereas the 110^100 Ma zircons have positive eHf(t) values.These observations suggest that melt^peridotite interactions at 80^170 Ma were induced by partial melting of recycled continental crust. The 48^64 Ma igneous zircons are characterized by negligible Ce anomalies, unusually high REE, U and Th contents, and positive eHf(t) values.These features imply that the melt^peridotite interactions at 48^64 Ma could be associated with a depleted mantle-derived carbonate melt or fluid.

Continental and Oceanic Crust Recycling-induced Melt^Peridotite Interactions in the Trans-North China Orogen: U^Pb Dating, Hf Isotopes and Trace Elements in Zircons from Mantle Xenoliths

Hf isotopic compositions of the standard zircons and baddeleyites used in U-Pb geochronology

A protocol was established for simultaneous measurements of zircon U-Pb ages and trace elements by LA-ICP-MS at spot sizes of 16–32 ?m. This was accomplished by introducing N2 into ICP to increase the sensitivity. The obtained U-Pb ages for zircon standards GJ-1, TEMORA and SK10-2 are consistent with the preferred values within about 1% uncertainty (2 σ ) by simple external calibration against zircon standard 91500. Different data reduction softwares could yield different uncertainties for calculation of U-Pb ages. The commercially available program GLITTER4.4 could apply an improper uncertainty calculation strategy, but it may yield artificial high precisions for single analyses. Our trace element analyses indicate that Si is not an ideal internal standard for zircon when calibrated against the NIST glasses. Calibration against the NIST glasses using Si as an internal standard, a systematic deviation of 10%–30% was found for most trace elements including Zr. However, the trace element compositions of zircon can be accurately measured by calibration against multiple reference materials with natural compositions (e.g., BCR-2G, BHVO-2G and BIR-1G), or calibration against NIST SRM 610 and using Zr as an internal standard. Analyses of two pieces of GJ-1 demonstrate that it is relatively homogenous for most trace elements (except for Ti).

Reappraisement and refinement of zircon U-Pb isotope and trace element analyses by LA-ICP-MS

There is a growing need for new zircon reference materials for in situ Hf-isotope analysis by laser ablation-multicollector inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS). In this contribution we document the results of a preliminary investigation of seven natural zircons, conducted in order to test their suitability in this regard. Solution MC-ICP-MS data on separated Lu and Hf fractions provided reference compositional data while the results of ca. 750 in situ LA-MC-ICP-MS analyses allowed assessment of potential micrometre-scale heterogeneity. On the basis of these analyses and additional relevant considerations such as availability, size and (Lu)Yb/Hf ratio, we suggest that, of the currently available zircons, Temora-2 and Mud Tank are most likely to provide robust reference materials for Hf isotope determinations both at the present time and into the future. The former has the advantage of also being well-characterised for U-Th-Pb systematics and suitable for in situ age determination, while the latter is the most readily available and is of very large grain size. Additional materials such as BR266, and 91500, although limited in supply, show more consistent Lu/Hf ratios and are thus of use in monitoring elemental fractionation during ICP-MS analysis.

A Preliminary Appraisal of Seven Natural Zircon Reference Materials for In Situ Hf Isotope Determination

This paper reports the results from a second characterisation of the 91500 zircon, including data from electron probe microanalysis, laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS), secondary ion mass spectrometry (SIMS) and laser fluorination analyses. The focus of this initiative was to establish the suitability of this large single zircon crystal for calibrating in situ analyses of the rare earth elements and oxygen isotopes, as well as to provide working values for key geochemical systems. In addition to extensive testing of the chemical and structural homogeneity of this sample, the occurrence of banding in 91500 in both backscattered electron and cathodoluminescence images is described in detail. Blind intercomparison data reported by both LA-ICP-MS and SIMS laboratories indicate that only small systematic differences exist between the data sets provided by these two techniques. Furthermore, the use of NIST SRM 610 glass as the calibrant for SIMS analyses was found to introduce little or no systematic error into the results for zircon. Based on both laser fluorination and SIMS data, zircon 91500 seems to be very well suited for calibrating in situ oxygen isotopic analyses.

Mj. Spicuzza

Papers

Further characterisation of the 91500 zircon crystal