Abstract A new method for studying the thermalization and transport of injected impurities at the edge of hot plasma, (considering the last closed magnetic surface, the free path is between 1 and 2 cm approx.) under no perturbative conditions, is presented. In the proposed technique, a Nd:YAG laser is used to ablate Li from the lithiated wall of the stellarator TJ-II. While the laser pulse allows for the analysis of the released species through laser induced breakdown spectroscopy (LIBS), its laser pulse also provides a time reference for the time-of-flight (TOF) measurements of the Li⁺ ions performed. This is done by positioning light detection systems sensitive to an intense Li II spectral line at different toroidal locations away from such a source. TOF times of tens to hundreds of microseconds are recorded. Then, by de-convolving the shape of the recorded light pulse, the velocity distribution of the lithium-ion during its thermalization with the background plasma can be extracted. From this velocity distribution, the ion temperature of the background ions and the toroidal rotation at the plasma periphery can be deduced. In contrast with conventional Doppler spectroscopy, this technique uses filter-scope detectors rather than high-spectral-resolution spectrometers thus a tradeoff between spectral and time or space resolution is required. Finally, preliminary results of the application of this novel technique are shown to validate this proof of principle.