The source of ions accelerated from high-intensity laser interactions with thin foil targets is investigated by coating a deuterated plastic layer either on the front, rear or both surfaces of thin foil targets. The originating surface of the deuterons is therefore known and this method is used to assess the relative source contributions and maximum energies using a Thomson parabola spectrometer to obtain high-resolution light-ion spectra. Under these experimental conditions, laser intensity of (0.5–2.5) × 1019 W cm−2, pulse duration of 400 fs and target thickness of 6–13 µm, deuterons originating from the front surface can gain comparable maximum energies as those from the rear surface and spectra from either side can deviate from Maxwellian. Two-dimensional particle-in-cell simulations model the acceleration and show that any presence of a proton rich contamination layer over the surface is detrimental to the deuteron acceleration from the rear surface, whereas it is likely to be less influential on the front side acceleration mechanism.