In this study, we compared the MZVI (Microscale Zero-Valent Iron) and NZVI (Nanoscale Zero-Valent Iron) for reactivity and mobility in a column to reduce nitrate, which is a major pollutant in Korea, and investigated the effect of operational parameters on the NZVI filled column. For the comparison of MZVI and NZVI, samples were collected for 990 minutes using fractionator in the similar operation conditions (MZVI 10g, NZVI 2g). The nitrate reduction efficiency of NZVI was about 5 times higher than that of MZVI, which was about 7.45% and 38.75% when using MZVI and NZVI, respectively. In the mobility experiment, the MZVI descended due to gravity while NZVI moved up with water flow due to its small size. Furthermore, the optimum condition of NZVI filled column was determined by changing the flow rate and pH. The amount of Fe ions was increased as the pH of the nitrate solution was lowered, and the nitrate removal rate was similar due to the higher yield of hydroxyl groups. The removal rate of nitrate nitrogen was stable while flow rate was increased from 0.5 mL/min to 2.0 mL/min (empty bed contact time: 2.26 min to 0.57 min). NZVI has a high reduction rate of nitrate, but it also has a high mobility, so both of reactivity and mobility need to be considered when NZVI is applied for drinking water treatment.
This study examined the treatment characteristics of hard-to-degrade pollutants such as TCE which are found in organic solvent and cleaning wastewater by nZVI that have excellent oxidation and reduction characteristics. In addition, this study tried to find out the degradation characteristics of TCE by Fenton-like process, in which H2O2 is dosed additionally.
In this study, different ratios of nZVI and H2O2, such as 1.0 mM : 0.5 mM, 1.0 mM : 1.0 mM, and 1.0 mM : 2.0 mM were used. When 1.0 mM of nZVI was dosed with 1.0 mM of H2O2, the removal efficiency of TOC was the highest and the first order rate constant was also the highest. When 1mM of nZVI was dosed with 0.5 mM of H2O2, the first order rate constant and removal efficiency were the lowest. The size of first order rate constant and removal efficiency was in the order of nZVI 1.0 mM : H2O2 1.0 mM > nZVI 1.0 mM : H2O2 2.0 mM > nZVI 1.0 mM : H2O2 0.5 mM > H2O2 1.0 mM > nZVI 1.0 mM. It is estimated that when 1.0 mM of nZVI is dosed with 1.0 mM of H2O2, Fe2+ ion generated by nZVI and H2O2 react in the stoichiometric molar ratio of 1:1, thus the first order rate constant and removal efficiency are the highest. And when 1.0 mM of nZVI is dosed with 2.0 mM of H2O2, excessive H2O2 work as a scavenger of OH radicals and excessive H2O2 reduce Fe3+ into Fe2+.
As for the removal efficiency of TOC in TCE by simultaneous dose and sequential dose of nZVI and H2O2, sequential dose showed higher first order reaction rate and removal efficiency than simultaneous dose. It is estimated that when nZVI is dosed 30 minutes in advance, pre-treatment occurs and nanoscale Fe0 is oxidized to Fe2+ and TCE is pre-reduced and becomes easier to degrade. When H2O2 is dosed at this time, OH radicals are generated and degrade TCE actively.