New methodologies have been developed for the determination of organotin and organolead compounds in environmental samples. Several high performance liquid chromatographic separations of organotin compounds have been tested and the best system (cation-exchange chromatography with methanol and a citrate buffer) employed for the determination of tributyltin (TBT), triphenyltin (TPhT), dibutyltin (DBT) and monobutyltin (MBT) in environmental samples. The coupling between high performance liquid chromatography (HPLQ and the inductively coupled plasma-mass spectrometer (ICP-MS) for this application has been modified to yield limits of detection of 0.44,0.26,1.4 and 0.23 ng. g-' as Sri for TBT, TPhT, DBT and MBT respectively. Different extraction procedures have been tested for the determination of organotin species in samples of environmental interest, such as sediments and biological materials. The values obtained for TBT, TPhT and DBT in the analysis of a mussel candidate reference material, CRM 477, have been incorporated in the certification campaign of this material. A liquid chromatographic separation for trimethyllead (TML) and triethyllead (TEL) has also been developed. Artificial rain water has been analysed for TML. The system proved to be valid for the determination of TML in this sample, even in the presence of high amounts of inorganic lead. Finally, isotope dilution analysis (IDA) was incorporated in the method. Tributyltin iodide (TBTI) and trimethyllead chloride (TMLCI), isotopically enriched in "Sn and "Pb, respectively, were synthesised. The mussel tissue CRM 477 was analysed with IDA-HPLC-ICPMS for TBT. As for the analysis without isotope dilution, the result obtained was incorporated in the certification campaign. The analysis with this methodology gave a better precision in the overall determination than external calibration analysis. Artificial rain water, at two different concentration levels, was analysed for TML with IDA-HPLC-ICP-MS. Better precision and accuracy was obtained for the analysis of this material with this method than when external calibration procedures were employed. IDA-HPLC-ICP-MS has proved to be a valid technique for the analysis of environmental samples. The technique simplifies the procedure, compensates for different sources of variability and, thus, the overall precision obtained in the analysis is improved compared to other calibration techniques.