Jitka Mikova

Chemical and phase composition of particles produced by laser ablation of silicate glass and zircon—implications for elemental fractionation during ICP-MS analysis

The chemical and phase compositions of particles produced by laser ablation (266 nm Nd:YAG) of silicate NIST glasses and zircon were studied by SIMS and HR-TEM techniques. The data suggest that the formation of phases of different mineralogy and/or chemical composition from the original sample at the ablation site can result in elemental fractionation (non-stoichiometric sampling) in material delivered to the ICP-MS for quantitative analysis. Evidence of the element fractionation is preserved in chemically zoned ejecta deposited around the ablation pit. The chemical composition and mineralogy of particles varies with particle size so that the efficiency of transport of particles also plays a role in elemental fractionation. During the first 250 pulses in a typical ablation experiment using a 266 nm laser, particle sizes are mainly <2.5 μm; thereafter they decrease to <0.3 μm. Pb and U are fractionated significantly during the ablation of both silicate glass and zircon. During the ablation of glass, both micron-sized, melt-derived, spherical particles, and nm-sized, condensate-derived particle clusters, are produced; the very smallest particles (<0.04 μm) have anomalously high Pb/U ratios. For zircon, both larger (0.2–0.5 μm) spherical particles and agglomerates of smaller (∼0.005 μm) particles produced by ablation are mixtures of amorphous and crystalline materials, probably zircon, baddeleyite (ZrO2) and SiO2. Evidence for thermal decomposition of zircon to baddeleyite and SiO2 is preserved in the wall of the ablation pit, and may lead to the commonly observed increase in Pb/U recorded during laser ablation ICP-MS analysis. It follows that a matrix-matched external calibration is essential for achieving highly precise and accurate laser (266 nm wavelength) ablation ICP-MS analysis of Pb and U in silicate samples.

The Fate of Atmospherically Derived Pb in Central European Catchments: Insights from Spatial and Temporal Pollution Gradients and Pb Isotope Ratios

Soils in polluted regions are generally regarded as a delayed, long-lasting source for Pb contamination of aquatic systems. Lead deposited on topsoil is slowly transported downward with particulate and colloidal organic matter, driven by infiltrating precipitation. Then, Pb is tightly retained in mineral soil. Lead export from catchments is extremely low and decoupled from the atmospheric input. We tested this hypothesis in 11 small catchments, differing in pollution levels. Input/ouput Pb fluxes were monitored for 14-15 years in an era of decreasing industrial Pb emission rates. Between 1996/1997 and 2010, Pb deposition fluxes decreased significantly, on average by 80%. At the beginning of the monitoring, Pb export constituted 2 to 58% of Pb input. At the end of the monitoring, Pb export constituted 2 to 95% of Pb input. Highly polluted sites in the northeast exported significantly more Pb than less polluted sites further south. The (206)Pb/(207)Pb isotope ratios of runoff (1.16) were identical to those of topsoil and present-day deposition, and different from mineral soil and bedrock. Lead isotope systematics and between-site flux comparisons indicated that a portion of the incoming Pb had a relatively short residence time in the catchments, on the order of decades.

Laser ablation ICPMS dating of zircons in Erzgebirge orthogneisses: evidence for Early Cambrian and Early Ordovician granitic plutonism in the western Bohemian Massif

U-Pb isotopic data obtained by laser ablation ICPMS analysis of nine zircons with centre to margin oscillatory growth zones from a K-feldspar-rich augen gneiss in the allochthonous Lower Crystalline Nappe of the Erzgebirge domain of the western part of the Bohemian Massif yield a concordia age of 524 ± 10 Ma (2 sigma). This Early Cambrian age represents the time of magmatic crystallization of the protolith of a representative, from near Měděnec, of the allochthonous “Red gneiss” whose igneous nature is shown by the presence of (deformed) xenoliths. Data from TIMS analysis of zircons with variable proportions of unzoned xenocrystic cores surrounded by oscillatory-zoned overgrowths point to magma derivation from upper Proterozoic, or older, rocks. Data obtained for five zircon grains from another “Red gneiss” in the Lower Crystalline Nappe (in the Klinovec anticline) plot below the concordia with the age of the one point that is near concordant being 519 ± 26 Ma (2 sigma). These data, together with internal features of the zircons, are consistent with Early Cambrian granitic plutonism also in this part of the Erzgebirge but with later Pb loss, possibly associated with considerable fluid movement during thrust nappe development. Another sample of a coarse-grained orthogneiss from the autochthonous St Catherine9s dome yielded a significantly younger Early Ordovician age of 480 ± 10 Ma (2 sigma) calculated from eight zircon analyses. However, three zircon grains from the same sample gave a significantly older near-concordant Late Proterozoic age of ca. 620 Ma. Provided that the age difference of ca . 40 Ma between orthogneisses from Měděnec - Klinovec and St Catherine9s dome holds also for other orthogneisses in the Erzgebirge, zircon U-Pb age data could be used to discriminate between allochthonous and autochthonous units in this region. The ca. 25 Ma difference between the Early Cambrian protolith age of the augen gneiss from near Měděnec determined by the laser ablation ICPMS technique and a previously reported older age of 550 ± 9 Ma for a nearby sample determined by the Pb-Pb evaporation technique is accounted for on the basis of the latter not being adequate for dating zircons with a small xenocrystic component. This study demonstrates the importance of high spatial resolution dating techniques, such as SHRIMP or laser ablation ICPMS, in dating zircons with complex growth history that are common in crustally-derived melts.