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.

The advanced oxidation treatment using persulfate and zero-valent iron (ZVI) has been evaluated as a very effective technology for remediation of soil and groundwater contamination. However, the high rate of the initial reaction of persulfate with ZVI causes over-consumption of an injected persulfate, and the excessively generated active species show a low transfer rate to the target pollutant. In this study, ZVI was modified using selenium with very low reactivity in the water environment with the aim of controlling the persulfate activation rate by controlling the reactivity of ZVI. Selenium-modified ZVI (Se/ZVI) was confirmed to have a selenium coating on the surface through SEM/EDS analysis, and low reductive reactivity to trichlroethylene (TCE) was observed. As a result of inducing the persulfate activation using the synthesized Se/ZVI, the persulfated consumption rate was greatly reduced, and the decomposition rate of the model contaminant, anisole, was also reduced in proportion. However, the final decomposition efficiency was rather increased, which seems to be the result of preventing persulfate over-consumption. This is because the transfer efficiency of the active species (SO4-∙) of persulfate to the target contaminant has been improved. Selenium on the surface of Se/ZVI was not significantly dissolved even under oxidation conditions by persulfate, and most of it was present in the form of Se/ZVI. It was confirmed that the persulfate activation rate could be controlled by controlling the reactivity of ZVI, which could greatly contribute to the improvement of the persulfate oxidation efficiency.

In this study, the reductive dechlorination of triclosan using zero-valent iron (ZVI, Fe0) and modified zero-valent iron (i.e., acid-washed iron (Aw/Fe) and palladium-coated iron (Pd/Fe)) was experimentally investigated, and the reduction characteristics were evaluated by analyzing the reaction kinetics. Triclosan could be reductively decomposed using zero-valent iron. The degradation rates of triclosan were about 50% and 67% when Fe0 and Aw/Fe were used as reductants, respectively, after 8 h of reaction. For the Pd/Fe system, the degradation rate was about 57% after 1 h of reaction. Thus, Pd/Fe exhibited remarkable performance in the reductive degradation of triclosan. Several dechlorinated intermediates were predicted by GC-MS spectrum, and 2-phenoxyphenol was detected as the by-product of the decomposition reaction of triclosan, indicating that reductive dechlorination occurred continuously. As the reaction proceeded, the pH of the solution increased steadily; the pH increase for the Pd/Fe system was smaller than that for the Fe0 and Aw/Fe system. Further, zero-order, first-order, and second-order kinetic models were used to analyze the reaction kinetics. The first-order kinetic model was found to be the best with good correlation for the Fe0 and Aw/Fe system. However, for the Pd/Fe system, the experimental data were evaluated to be well fitted to the second-order kinetic model. The reaction rate constants (k) were in the order of Pd/Fe > Aw/Fe > Fe0, with the rate constant of Pd/Fe being much higher than that of the other two reductants.

In this study, the reductive decolorization of three acid and basic dyes using modified zero-valent iron (i.e., acid-washed iron (Aw/Fe) and palladium coated iron (Pd/Fe)) at various pH conditions (pH 3 5) was experimentally investigated and the decolorization characteristics were evaluated by analyzing the absorbance spectra and reaction kinetics. In the case of acid dyes such as methyl orange and eriochrome black T, color removal efficiencies increased as initial pH of the dye solution decreased. However, the color removal of methylene blue, a basic dye, was not affected much by the initial pH and more than 70% of color was removed within 10 min. During the decolorization reaction, the absorbance of methyl orange (λmax = 464 nm) and eriochrome black T (λmax = 528 nm) decreased in the visible range but increased in the UV range. The absorbance of methylene blue (λmax = 664 nm) also decreased gradually in the visible range. Pseudo-zero order, pseudo-first order, and pseudo-second order kinetic models were used to analyze the reaction kinetics. The pseudo-second order kinetic model was found to be the best with good correlation. The decolorization reaction rate constants (k2) of methylene blue were relatively higher than those of methyl orange and eriochrome black T. The reaction rate constants of methyl orange and eriochrome black T increased with a decrease in the initial pH.

In order to treat groundwater containing high levels of nitrate, nitrate reduction by nano sized zero-valent iron (nZVI) was studied using batch experiments. Compared to nitrate removal efficiencies at different mass ratios of nitrate/Fe0, the removal efficiency at the mass ratio of 0.02% was the highest(54.59%). To enhance nitrate removal efficiency, surface modification of nZVI was performed using metallic catalysis such as Pd, Ni and Cu. Nitrate removal efficiency by Cu-nZVI (at catalyst/Fe0 mass ratio of 0.1%) was 66.34%. It showed that the removal efficiency of Cu-nZVI was greater than that of the other catalysts. The observed rate constant (kobs) of nitrate reduction by Cu-nZVI was estimated to 0.7501 min-1 at the Cu/Fe mass ratio of 0.1%. On the other hand, TEM images showed that the average particle sizes of synthetic nZVI and Cu-nZVI were 40~60 and 80~100 nm, respectively. The results imply that catalyst effects may be more important than particle size effects in the enhancement of nitrate reduction by nZVI.

광산배수가 지표에 노출되거나 주변 수계로 유입됨에 따라 나노크기의 철 교질물질이 형성되며, 이러한 철 교질물질은 심미적 오염을 발생시킬 뿐만 아니라 수생태계에도 악영향을 미친다. 이를 제어하기 위해 철 나노물질의 거동특성을 파악하는 것이 매우 중요한데, 아직까지 이에 대한 연구가 미흡하다. 본 연구는 영가철과 자철석을 이용하여 배경용액의 pH와 조성, 그리고 자연유기물에 따른 철 나노물질의 거동특성을 고찰하기 위해 수행되었다. 이를 위해 동적광산란분석기를 이용하여 철 나노물질의 입자크기와 표면 제타전위를 측정하였으며, DLVO (Derjaguin, Landau, Verwey, and Overbeek) 이론에 적용하여 응집 및 분산 등의 거동특성을 비교하였다. 철 나노물질은 영전하점 pH 근처에서는 입자간의 전기적 인력으로 인한 응집이 발생되며, 그보다 pH가 낮거나 높으면 전기적 반발력에 의해 분산이 잘되는 것을 확인하였다. 배경용액 내 양이온이 음이온보다 거동특성에 더 큰 영향을 끼치는 것을 확인하였으며, 특히 1가 양이온보다 2가 양이온이 입자표면간의 전기적인 인력 및 반발력에 더 큰 영향을 주는 것을 알 수 있었다. 수용상의 자연유기물은 철 나노물질을 코팅함으로써 표면을 음전하로 띠게 하여 분산이 잘 되게 하는 것을 확인하였다. 동일한 환경조건에서 자철석보다 영가철이 응집이 더 잘 되는 것으로 나타났는데, 이는 영가철의 낮은 안정성과 빠른 반응성으로 인해 철 산화물로 변질되기 때문인 것으로 판단된다.

경제성장과 급격한 산업화는 생활수준을 향상시켰으며 인구증가와 맞물려 세계적으로 물 사용량을 증가시켰고 결과적으로 하수슬러지의 발생량을 증가 시켰다. 국내의 하수도보급률을 85%를 상회하며 이로 인해 발생되는 하수슬러지의 양은 2006년 2,717,790 톤/년에서 2013년 말 기준으로 3,995,290 톤/년으로 3배가량 증가하였으며 하수슬러지의 양은 지속적으로 증가할 것으로 예상된다. 하수슬러지를 처리하기 위해 선진국에서는 육상 처리를 전제로 여러 가지 처리 기술들을 개발하고 있으며 국내에서도 여러 가지의 처리 방법이 연구되고 있는 상황이다. 하수슬러지를 처리하는 방법으로는 매립과 해양투기 이외에 소각, 용융, 탄화, 퇴비화, 시멘트 자원화 등의 여러 기술 등이 있다. 하지만 기술적, 경제적인 이유로 국내에서는 쉽게 적용되지 못하고 있는 실정이다. 이러한 문제를 해결하기 위하여 환경부에서는 공공하수처리장의 혐기성 소화조 효율을 향상시킴으로서 하수슬러지의 감량화를 통한 바이오가스의 생산량 증대를 위한 다양한 전처리 기술들이 연구되고 있다. 혐기성 소화단계는 가수분해, 산생성, 초산생성, 메탄생성 단계로 구분되어 있으며 이 중 가수분해 단계는 혐기성 소화의 율속 단계로서 혐기성 소화 전체 과정의 소화효율과 속도를 조절한다. 따라서 본 연구에서는 공기주입과 영가철(ZVI)을 이용한 산화 반응을 이용하여 하수슬러지속 세포벽을 파괴시켜 세포내의 각종 유기물을 용출시킨 후 가수분해 단계 촉진을 위한 가용화를 이용한 전처리 공정을 적용하고자 한다. 실험방법으로 슬러지 1kg 당 0.015 L/hr의 사전 공기 주입 후 0.1%, 0.5%, 1%, 1.5%, 2%, 3%의 영가철(ZVI)을 투입하여 전처리를 실시한다. 전처리 실시 후 실험결과 가용화율은 영가철(ZVI) 1.5% 투입시에 85%까지 상승하였으며 2% 투입 이후 부터는 더는 증가하지 않았다. 이를 통하여 산소주입과 영가철(ZVI)을 이용한 전처리가 하수슬러지의 가용화에 효과가 있는 것으로 나타났으며, 최종적으로 바이오가스 생산량 증가에 효과가 있을 것으로 판단된다. 향후 추가실험을 통해 하수슬러지의 오염부하의 저감 가능성을 평가하고 공기주입과 영가철(ZVI)을 이용한 전처리가 바이오가스 생성에 방해가 되는 H2S의 생성 억제에 미치는 영향에 대하여 연구하고자 한다.