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 <2.5μm; 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 (ZrO 2) 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.