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Considerable leaching of alkali metals was documented, both in concrete samples exposed to accelerated laboratory testing and field samples. CWE allowed to quantitatively determine the free alkali metal profiles as a function of the depth. However, CWE cannot account for the changes in the paste content towards a cast surface leading to a seemingly increase in alkali metals. The μXRF allowed to distinguish paste and aggregates. It allowed thereby to determine qualitative Na and K profiles in the cement paste phase of the concrete samples. The laboratory exposed samples showed a clear leaching profile into a depth of about 15 mm after 21 weeks of exposure at 60°C. Corresponding numbers for the 12 years field exposed cube were 50-60 mm. Alkali sorption by alkali silica gel was detected using the μXRF. For the laboratory exposed samples, the prisms prepared with Portland fly ash cement leached less alkali compared to the prisms prepared with ordinary Portland cement, as expected. The leaching in the middle of the prisms estimated based on the μXRF profiles agreed rather well with the level of alkali leaching determined based on the analysis of the leachate (i.e. the water below the samples during exposure).