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The objective of this study was to develop a method for measuring the mobility of persistent organic pollutants in the solid phase of soils within the context of environmental pollution risk assessment. A new diffusive probe, purposely designed by adapting the diffusive gradient technique method, measures labile organic species by immobilizing them after diffusion through a thin deionized water layer. The measure of the mass accumulated is used to calculate the flow of pollutant from solid phase to pore water. Naphthalene was chosen as a model persistent organic pollutant. The probe was calibrated at different temperatures and was then tested in several microcosms at different porosity and reactivities with naphthalene (one clay soil, two sandy soils and one natural soil). The probe response showed good agreement with the expected different abilities of the solid phases in restoring the solution phase. The concentration of naphthalene in the pore water was well buffered by rapid equilibria with the solid phase in the investigated natural soil. In contrast, pore water concentration in the sandy soils decreased rapidly and the flow was slackened, especially for the sandy soil with finer particles. In clay, only a fraction of the total naphthalene content was present in the labile fraction, while the remaining was tightly bound and was not released to the pore water. Therefore, this first stage of testing points out that the diffusive gradient technique, if optimized, can properly quantify the mobility of organic pollutants in soil.