Atmospheric pressure x-ray spectroscopy techniques based on soft x-ray excitation can provide interface-sensitive chemical information about a solid surface immersed in a gas or liquid environment. However, x-ray illumination of such dense phases can lead to the generation of considerable quantities of radical species by radiolysis. Soft x-ray absorption measurements of Cu films in both air and aqueous alkali halide solutions reveal that this can cause significant evolution of the Cu oxidation state. In air and NaOH (0.1M) solutions, the Cu is oxidized towards CuO, whilst the addition of small amounts of CH3OH to the solution leads to reduction towards Cu2O. For Ni films in NaHCO3 solutions, the oxidation state of the surface is found to remain stable under x-ray illumination, and can be electrochemically cycled between a reduced and oxidized state. We provide a consistent explanation for this behavior based on the products of x-ray induced radiolysis in these different environments, and highlight a number of general approaches that can mitigate radiolysis effects when performing operando x-ray measurements.