Hard amorphous films of a-C:H and a-C:D were deposited by a rf glow discharge in either CH4 or CD4 . By ion bombardment with protons and deuterons, the H/D exchange process was studied as function of the bombardment fluence by means of depth profile measurements. The local hydrogen and deuterium contents are not adding up to a constant ‘‘saturation’’ value: the local mixing model is not valid. Instead of that an initial depletion appears, which depends on the incident energy of the ions. At higher fluences, the total (H+D):C ratio tends to increase again, due to an increasing influence of the deposition process. This demonstrates a structural difference between a-C:H films and hydrogen-saturated layers of implanted carbon.