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Laser Ablation - Inductively Coupled Plasma - Mass Spectrometry (LA-ICP-MS) is a powerful analytical technique for the direct elemental analysis of solid samples, with spatial resolution down to a few microns However, calibration remains the limiting factor in obtaining quantitative analysis by LA-ICP-MS for a wide range of sample types. No universal method exists as yet and the ones that are currently used tend to employ matrix-matched solid standards Matrix-matched solid standards are not available for many types of sample, such as polymers, biological materials, fluid inclusions, etc The need for a universal method of calibration that involves standards that are easy to prepare and suitable for any type of sample is required. Additional to matrix-matching, internal standards are widely used in LA-ICP-MS for quantitative analyses The internal standard compensates for the different ablation yields from the sample and the standard and for the laser shot to shot variation. Given that the use of an internal standard is required to obtain reliable results, the need for matrix-matching might be regarded as questionable This project has focused on the development and application of a new method of calibration for LA-ICP-MS. It involves the use of aqueous standards whose absorption characteristics are modified by the addition of a chromophore to the solution. Additives were selected for ablation with KrF excimer, and Nd.YAG lasers The influence of the additive concentration on the ablation yield was investigated for different laser energies. Response curves were obtained showing that as the additive concentration was increased, less energy was required to ablate the modified standard solutions efficiently. A general procedure was then defined for the preparation and use of the modified standard solutions for a given sample. The new method of calibration was used for the quantitative analysis of different sample types· low density polyethylene (LDPE), polyketone (PK), polyethylene thin film as well as gels contained in the thin film, and stainless steel. Investigations were carried out on the mechanism of ablation of the modified standard solutions. It appeared that the ablation proceeded by a three-step process leading ultimately to nebulisation of the bulk liquid.

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