A method for arsenic speciation in soils is developed, based on extraction with a mixture of 1 mol l(-1) of phosphoric acid and 0.1 mol l(-1) of ascorbic acid, and further measurement with the coupling liquid chromatography (LC)-ultraviolet (UV) irradiation-hydride generation (HG)-inductively coupled plasma mass spectrometry (ICP/MS). The stability of the arsenic species in the extracts is also studied. The speciation method applied to several Spanish agricultural contaminated soils from the Aznalcollar zone shows that arsenate is the main species in all the soils analysed and that in some samples arsenite and methylated species could also be detected. The determination of the "pseudototal" arsenic in these soils, obtained by applying extraction with aqua regia (ISO Standard 11466), is also carried out. Both the speciation method and the aqua regia method are applied to several certified reference materials (CRMs) in which total arsenic content is certified. Finally, the same LC-UV-HG coupling with atomic fluorescence spectrometry (AFS) detection reveals to be a valid coupling system to perform arsenic speciation in the soils according to its fair quality parameters and easy utilisation.