Apparatuses and methods of measuring a hydrogen diffusivity of a metal structure including during operation of the metal structure, are provided. A hydrogen charging surface is provided at a first location on an external surface of the structure. In addition, a hydrogen oxidation surface is provided at a second location adjacent to the first location on the external surface of the structure. Hydrogen flux is generated and directed into the metal surface at the charging surface. At least a portion of the hydrogen flux generated by the charging surface is diverted back toward the surface. A transient of the diverted hydrogen fluxes measured, and this measurement is used to determine the hydrogen diffusivity of the metal structure in service.