The aim of this work was to determine the concentrations and isotopic compositions of plutonium and uranium in environmental samples for safeguards purposes. An analytical method was developed with a plutonium and uranium separation procedure based on extraction chromatography (using 2mL TEVA and UTEVA columns) and detection with a quadrupole ICP-MS applying an ultra-sonic nebulizer coupled with a membrane desolvation system. Starting from blank swipes, the background equivalent concentration (BEC) was 8fg for (239)Pu and 1ng (238)U. The method was successfully applied to certified reference materials as well as to round robin samples obtained in the framework of the inter-laboratory exercise program, promoted by the Brazilian-Argentine Agency for Accounting and Control of Nuclear Materials (ABACC), together with the US Department of Energy (USDOE). After the introduction of an additional ion-exchange separation step, the methodology was applied to the IAEA-384 sediment reference sample with precise and accurate total plutonium and uranium, (240)Pu/(239)Pu, (241)Pu/(239)Pu, (234)U/(238)U and (235)U/(238)U atomic ratio results.