Uranium mining activities expose uranium ore and mine tailings to the surface environment, where the release of radionuclides is facilitated by weathering at rates exceeding those typically found in nature. Therefore, close to former uranium mining sites, radionuclides and especially uranium concentrations in water may surpass local background levels. The methodology proposed herein, entails coupling, gamma-ray mapping, water sampling and chemical analyses including DGT (Diffusive Gradient in Thin Film) measurements, provides new insights into describing the environment of the La Commanderie site (France). Gamma-ray mapping allows identifying water seepage, output from a waste rock pile, as a potential pathway for radionuclides into the environment. Water seepage monitoring has shown: a low pH value (4.2), high sulfate content (179 mg.L−1) and high uranium concentrations of up to 436 μg.L−1. These recordings indicate that an acid mining drainage (AMD) process is occurring inside or under the oxidized parts of the waste rock pile. Monitoring data over three flow periods revealed the release of the highest uranium concentrations during a high-flow period downstream of the site, which is compliant with local regulations. The AMD process is also responsible for the release of significant amounts of Fe, Mn and As within the immediate environment in both dissolved and particulate forms. Changes in dissolved oxygen concentration and redox potential during low flow periods, modify the speciation of Fe (in AMD waters) which acts as a scavenger for other elements such as As, Mn and U. The use of DGT under environmental conditions, and specifically AMD waters, seems to be relevant in comparison to filtered spot water sampling strategies. Moreover, based on DGT measurements, the dissolved part of the released uranium is considered as labile with concentrations above the environmental standards for freshwater organisms.