The localization and identification of arsenic compounds in terrestrial plants are important for the understanding of arsenic uptake, transformation and translocation within these organisms, and contributes to our understanding of arsenic cycling in the environment. High performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC-ICP-MS), and X-ray absorption near-edge structure (XANES) analysis identified arsenite, arsenate and arsenic(III)-sulphur compounds in leaf, stem and root sections of Rhaphanus sativus (radish) plants grown in both arsenic contaminated mine waste, and arsenic amended liquid cultures. The total arsenic distribution was similar between the plants grown in mine waste and those grown hydroponically. Arsenate was the predominant form of arsenic available in the growth mediums, and after it was taken up by roots, X-ray absorption spectroscopy (XAS) imaging indicated that some of the arsenate was transported to the shoots via the xylem. Additionally, arsenate was reduced by the plant and arsenic(III)-sulphur compound(s) accounted for the majority of arsenic in the leaf and stem of living plants. In this study the application of synchrotron techniques permitted the identification of arsenic(III)-sulphur species which were "invisible" to conventional HPLC-ICP-MS analysis.