Nuclear plant stainless steel can become contaminated by radionuclides during normal operation whereby the final disposition of these materials then becomes a major decommissioning challenge to address. Characterisation of the chemical and metallurgical processes that underpin contamination is essential in consideration of developing cost effective decontamination and prevention methods, as are in situ measurement techniques that allow assessment of contamination. To address these issues, contamination experiments to simulate the nitric acid-based reprocessing streams of the PUREX (Plutonium Uranium Redox Extraction) process, and alkaline spent fuel storage ponds were investigated. Solution and surface spectroscopic measurements were performed to characterise the sorption behaviour of stable analogues of two high yield fission products, Sr-90 and Cs-137, on as received and 30 % cold rolled AISI Type 304 stainless steel, respectively. In addition Laser Induced Breakdown Spectroscopy (LIBS) was also investigated as a standoff contamination assessment technique. Fission product accumulation was modelled to a second order kinetic fit that considers chemisorption, typically to a hydrous metal oxide surface, as rate controlling. This process is observed to be independent of solution composition and strain processing regime. This behaviour reflects complexation to the passivating surface chromium oxide film, and as determined by depth elemental analysis, effectively inhibits contaminant migration into the bulk material. Environment chemistry and microstructural variables that destabilise the Cr-rich passive film however reduces the passive layer capabilities to effectively inhibit fission product bulk diffusion. The importance of corrosion phenomena towards radionuclide sorption processes necessitates the consideration of metallurgical and chemical factors during the implementation of decontamination approaches to treat affected plant material at nuclear licenced sites. LIBS was found to be a satisfactory technique for measurement of Sr sorbed to steel but Cs could not be detected at the concentrations used in this experimentation. Furthermore, EDX and TOF-SIMS elemental mapping indicated ablated material may be redistributed into the crater profile during elemental analysis. This process has clear implications for the deployment of LIBS for in situ characterisation of nuclear materials as the uncontrolled redistribution of radioactive material certainly violates decommissioning principles.