Upstream of the efficiency of proton or carbon ion beams in cancer therapy, and to optimize hadrontherapy results, we analysed the chemistry of Fricke solutions in track-end of 64-MeV protons and 1.14-GeV carbon ions. An original optical setup is designed to determine the primary track-segment yields along the last millimetres of the ion track with a sub-millimetre resolution. The Fe ³⁺ -yield falls in the Bragg peak to (4.9 ± 0.4) × 10 ^-7 mol/J and 1.9 × 10 ^-7 mol/J, under protons and carbon ions respectively. Beyond the Bragg peak, a yield recovery is observed over 1 mm for proton beams. It is attributed to the intermediate-LET of protons in this region where their energy decreases and energy distribution becomes broader, in relation with the longitudinal straggling of the beam. Consequently to this LET decrease in the distal part of the Bragg peak, Fe ³⁺ -yield increases. For the first time, this signature is highlighted at the chemical level under proton irradiation. Nevertheless, this phenomenon is not identified for carbon ion beams since their straggling is lower. It would need a greater spatial resolution to be observed.