The application of laser ablation-inductively coupled plasma-mass spectrometry to in situ U–Pb zircon geochronology

Zircon is the main mineral in the majority of igneous and metamorphic rocks with Zr as an essential structural constituent. It is a host for significant fractions of the whole-rock abundance of U, Th, Hf, and the REE (Sawka 1988, Bea 1996, O’Hara et al. 2001). These elements are important geochemically as process indicators or parent isotopes for age determination. The importance of zircon in crustal evolution studies is underscored by its predominant use in U-Th-Pb geochronology and investigations of the temporal evolution of both the crust and lithospheric mantle. In the past decade an increasing interest in the composition of zircon, trace-elements in particular, has been motivated by the effort to better constrain in situ microprobe-acquired isotopic ages. Electron-beam compositional imaging and isotope-ratio measurement by in situ beam techniques—and the micrometer-scale spatial resolution that is possible—has revealed in many cases that single zircon crystals contain a record of multiple geologic events. Such events can either be zircon-consuming, alteration, or zircon-forming and may be separated in time by millions or billions of years. In many cases, calculated zircon isotopic ages do not coincide with ages of geologic events determined from other minerals or from whole-rock analysis. To interpret the geologic validity and significance of multiple ages, and ages unsupported by independent analysis of other isotopic systems, has been the impetus for most past investigations of zircon composition. Some recent compositional investigations of zircon have not been directly related to geochronology, but to the ability of zircon to influence or record petrogenetic processes in igneous and metamorphic systems.

Sedimentary rocks may also contain a significant fraction of zircon. Although authigenic zircon has been reported (Saxena 1966, Baruah et al. 1995, Hower et al. 1999), it appears to be very rare and may in fact be related to …

/pdf/the-composition-of-zircon-and-igneous-and-metamorphic-1g2xfkpi4l.pdf

The Composition of Zircon and Igneous and Metamorphic Petrogenesis

In situ analysis of major and trace elements of anhydrous minerals by LA-ICP-MS without applying an internal standard

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

Iolite is a non-commercial software package developed to aid in the processing of inorganic mass spectrometric data, with a strong emphasis on visualisation versus time of acquisition. The goal of the software is to provide a powerful framework for data processing and interpretation, while giving users the ability to implement their own data reduction protocols. It is intended to be highly interactive, providing the user with a complete overview of the data at all stages of processing, and allowing the freedom to change parameters and reprocess data at any point. The program presents a variety of windows for the selection and viewing of data versus time, as well as features for the generation of X-Y plots, summary reports and export of data. In addition, it is capable of generating X-Y images from laser ablation rasters, and combining information from up to four separate elemental concentrations (intensities of red, green and blue, and the z-axis) in a false-colour three-dimensional image. By virtue of its underlying computing environment—Igor Pro—Iolite is capable of processing very large datasets (i.e., millions of timeslices) rapidly, and is thus ideal for the interrogation of multi-hour sessions of laser ablation data that can not be easily manipulated in conventional spreadsheet applications, for example. It is also well suited to multi-day sessions of solution-mode inductively-coupled plasma mass spectrometer (ICPMS) or thermal ionisation mass spectrometer (TIMS) data. A strong emphasis is placed on the interpolation of parameters that vary with time by a variety of user selectable methods including smoothed cubic splines. Data are processed on a timeslice-by-timeslice basis, allowing outlier rejection and calculation of statistics to be employed directly on calculated results. This approach can reduce the risk of processing biases associated with the manipulation of integrated datasets, while also allowing the implementation of more complex data reduction methods.

Iolite: Freeware for the visualisation and processing of mass spectrometric data

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) produces complex, time-dependent signals. These require significantly different treatment both during data acquisition and reduction from the more steady-state signals produced by solution sample introduction. This paper discusses, in detail, data acquisition and reduction considerations in LA-ICP-MS analysis. Optimum data acquisition parameters are suggested. Equations are derived for the calculation of sample concentrations and LOD when time-resolved data acquisition is employed, sensitivity calibration is obtained from reference materials with known analyte concentrations and naturally occurring internal standards are used to correct for the multiplicative correction factors of drift, matrix effects and the amount of material ablated and transported to the ICP.

Inter-laboratory note. Laser ablation inductively coupled plasma mass spectrometric transient signal data acquisition and analyte concentration calculation

ICP-MS — A powerful tool for high-precision trace-element analysis in Earth sciences: Evidence from analysis of selected U.S.G.S. reference samples

A laser ablation microprobe (LAM) sample-introduction system, designed for in sira microsampling of minerals in petrographic sections, has been interfacedto anlnductively CoupledPlasma-Mass Spectrometer(ICP-MS). TheLAM consists of aQ-switched Nd:YAG laser with power attenuation and steering optics to guide the laser beam through the phototube of a petrographic microscope, where it is focused onto the petrographic section contained in a sample cell. The response of rock-forming minerals to ablation is related to their absorptivity of the 1064 nm wavelength of the laser beam (a function of the proportion of transifion elements, especially Fe), and their physical properties, particularly cleavage and tenacity. Minerals with a high absolptivity can generally be ablated controllably in thin section. In minerals with low absorptivity, catastrophic ablation may occur due to absorption at interfaces beneath the mineral surface, particularly at the mineral glass slide interface in standard thin sections. Most minerals can be ablated controllably in unsupported polished wafers, grain mounts and polished blocks, where ablation pits with diameten of 2A-40 pm can be achieved routinely. In addition, the ability of the LAM to bore allows production of vertical profiles of element concentrations at a much finer spatial resolution. Comparison of LAMand solution-ICP-MS analyses of titanite, zircon, apatite, uraninite, and garnet separates demonstrates that a simple scheme of calibration employing.a spiked NBS silicate glass reference material, using major-element intemal standards to correct for differences in ablation yield, drift, and matrix effects, provides good accuracy and precision (RSD < 107o, at concentrations > 60 ppm) for a diverse suite of elements. Routine limits of detection are about 0.5 ppm.

The application of laser-ablation microprobe; inductively coupled plasma-mass spectrometry (LAM-ICP-MS) to in situ trace-element determinations in minerals

Inductively coupled plasma-mass spectrometric analysis of geological samples: A critical evaluation based on case studies

The design, operation and role of the laser-ablation microprobe coupled with an inductively coupled plasma-mass spectrometer (LAM- ICP-MS) in the Earth sciences

Henry P. Longerich

Papers

Inter-laboratory note. Laser ablation inductively coupled plasma mass spectrometric transient signal data acquisition and analyte concentration calculation

ICP-MS — A powerful tool for high-precision trace-element analysis in Earth sciences: Evidence from analysis of selected U.S.G.S. reference samples

The application of laser-ablation microprobe; inductively coupled plasma-mass spectrometry (LAM-ICP-MS) to in situ trace-element determinations in minerals

Inductively coupled plasma-mass spectrometric analysis of geological samples: A critical evaluation based on case studies

The design, operation and role of the laser-ablation microprobe coupled with an inductively coupled plasma-mass spectrometer (LAM- ICP-MS) in the Earth sciences