Continuous gravity-fed column experiments using the methylene blue (MB) discoloration method were performed to characterize the suitability of a pozzolan (PZ) specimen as alternative admixing aggregate for metallic iron filters (Fe0-filters). Investigated systems were: (i) pure sand, (ii) pure PZ, (iii) pure Fe0, (iv) Fe0/sand, (v) Fe0/PZ, and (vi) Fe0/sand/PZ. The volumetric proportion of Fe0 was 25%. The volumetric proportions of the Fe0/sand/PZ system was 25/45/30. The initial MB concentration was 2.0 mg·L−1, 6.0 g of Fe0 was used, and the experiments lasted for 46 days. The individual systems were fed with 3.9 to 8.4 L (7.80 to 16.69 mg of MB) and were characterized by the time-dependent changes of: (i) the pH value, (ii) the iron breakthrough, (iii) the MB breakthrough, and (iv) the hydraulic conductivity. Results showed that the Fe0/sand/PZ system was the most efficient. This ternary system was also the most permeable and therefore the most sustainable. The suitability of MB as a powerful operative indicator for the characterization of processes in the Fe0/H2O system was confirmed. The tested PZ is recommended as an alternative material for efficient but sustainable Fe0 filters.