• 상하수도학회지
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• 제23권4호
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• pp.471-479
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• 2009

A Nanoscale Zero-Valent Iron(NZVI) was modified to build a reactor system to treat nitrate. Shell layer of the NZVI was modified by slow exposure of the iron surface to air flow, which produced NZVI particles that are resistant to aerial oxidation. A XANES (X-ray Absorption Near-Edge Structure) analysis revealed that the shell consists of magnetite ($Fe_3O_4$) dominantly. The shell-modified NZVI(0.5 g NZVI/ 120 mL) was able to degrade more than 95% of 30 mg/L of nitrate within $30 hr^{-1}$ ( pseudo first-order rate constant($k_{SA}$) normalzed to NZVI surface area ($17.96m^2/g$) : $0.0050L{\cdot}m^{-2}{\cdot}hr^{-1}$). Ammonia occupied about 90% of degradation products of nitrate. Nitrate degradation efficiencies increased with the increase of NZVI dose generally. Initial pH values of the reactor systems at 4, 7, and 10 did not affect nitrate removal rate and final pH values of all experiments were near 12. Nitrate removal experiments by using the shell-modified NZVI immobilized on a cellulose acetate (CA) membrane were also conducted. The nitrate removal efficiency of the CA membrane supported NZVI ($k_{SA}=0.0036L{\cdot}m^{-2}{\cdot}hr^{-1}$) was less than that of the NZVI slurries($k_{SA}=0.0050L{\cdot}m^{-2}{\cdot}hr^{-1}$), which is probably due to less surface area available for reduction and to kinetic retardation by nitrate transport through the CA membrane. The detachment of the NZVI from the CA membrane was minimal and impregnation of up to 1 g of NZVI onto 1 g of the CA membrane was found feasible.

• 한국지하수토양환경학회지:지하수토양환경
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• 제22권2호
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• pp.17-25
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• 2017

The efficiency and mechanism of electrochemical phenol oxidation using persulfate (PS) and nanosized zero-valent iron (NZVI) were investigated. The pseudo-first-order rate constant for phenol removal by the electrochemical/PS/NZVI ($1mA^*cm^{-2}/12$ mM/6 mM) process was $0.81h^{-1}$, which was higher than those of the electrochemical/PS and PS/NZVI processes. The electrochemical/PS/NZVI system removed 1.5 mM phenol while consuming 6.6 mM PS, giving the highest stoichiometric efficiency (0.23) among the tested systems. The enhanced phenol removal rates and efficiencies observed for the electrochemical/PS/NZVI process were attributed to the interactions involving the three components, in which the electric current stimulated PS activation, NZVI depassivation, phenol oxidation, and PS regeneration by anodic or cathodic reactions. The electrochemical/PS/NZVI process effectively removed phenol oxidation products such as hydroquinone and 1,4-benzoquinone. Since the electric current enhances the reactivities of PS and NZVI, process performance can be optimized by effectively manipulating the current.

• 상하수도학회지
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• 제32권3호
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• pp.243-251
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• 2018

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.

• 한국지하수토양환경학회지:지하수토양환경
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• 제13권6호
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• pp.93-102
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• 2008

본 연구는 대기중에서 안정한 나노크기 영가철을 제조한 후 그 특성을 평가하기 위해 수행되었다. XRD, XPS 분석을 통해 인위적으로 4, 8, 12 mL/min 유량의 공기 접촉을 통해 형성된 shell의 두께는 5 nm로 모두 유사한 것으로 확인되었고, shell의 성분은 magnetite(${Fe_3}{O_4}$), maghemite(${\gamma}-{Fe_2}{O_3}$)가 주성분임을 확인할 수 있었다. 4, 8, 12 mL/min의 접촉 공기 유량에 따른 shell의 명확한 성분 및 두께 변화는 확인할 수 없었다. 반면 대기 중에서 공기와 급속으로 접촉시킨 나노크기 영가철의 경우는 TEM 분석 결과 shell 층이 확인되지 않았다. 4, 8, 12 mL/min의 유량으로 공기 접촉된 나노크기 영가철의 TCE 분해능($k_{obs}$= 0.111, 0.102, and 0.086 $hr^{-1}$) 또한 큰 차이를 보이지 않았으며, fresh한 나노크기 영가철에 비해서는 약 80%의 분해효율을 나타내었다. Fresh한 나노크기 영가철 및 4 mL/min과 급속으로 공기 접촉시킨 나노크기 영가철을 물속에서 1일 동안 물과 접촉시킨 후 분해능을 평가한 실험에서는 공기 접촉 후 바로 분해 실험한 것 보다 분해능이 모두 향상되었다. 이는 물과의 반응을 통해 shell 층이 벗겨져 순수한 Fe(0)와 TCE의 접촉이 빨라져서 일어난 결과로 판단되어진다. 또한 각각 1주일과 2달간 대기 중에서 방치한 후 분해 실험한 결과 공기 접촉 후 바로 분해 실험한 결과와 비교해서 분해능이 90%와 50%로 감소하였다. 따라서 본 연구결과 일정 유량으로 공기 접촉 시킨 나노크기 영가철은 대기 중 산소에 안정하기 때문에 실제 현장 적용에 유리할 것으로 판단된다.

• 한국지하수토양환경학회지:지하수토양환경
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• 제22권1호
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• pp.41-48
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• 2017

Persulfate (PS) activated with nanosized zero-valent iron (NZVI) was tested as a reagent to remove phenol from groundwater. Batch degradation experiments indicated that NZVI/PS molar ratios between 1 : 2 and 1 : 5 were appropriate for complete removal of phenol, and that the time required for complete removal varied with different PS and NZVI dosages. Chloride ions up to 100 mM enhanced the phenol oxidation rate, and nitrate of any concentration up to 100 mM did not significantly affect the oxidation rate. NZVI showed greater performance than ferrous iron did as an activator for PS. A by-product was formed along with phenol degradation but subsequently was completely degraded, which showed the potential to attain mineralization with the NZVI/PS system. Tests with radical quenchers indicated that sulfate radicals were a predominant radical. The results of this study suggest that NZVI is a promising activator of PS for treating contaminated groundwater.

• Advances in environmental research
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• 제3권1호
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• pp.29-43
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• 2014

Pharmaceutical wastewater effluents are well known for their difficult elimination by traditional biotreatment methods and their important contribution to environmental pollution due to its fluctuating and recalcitrant nature. OTC is one of the nonbiodegradable antibiotics that makes antibiotic-resistant, so it can make be high risk for environment. NZVI can be a good choice for removal of OTC in aqueous solution. Response surface methodology (RSM) was used to optimize the amounts of NZVI and OTC to be used at pH 3 and under 200 W, UV-A irradiation. The responses were removal percent of absorption at 290 and 348 nm, TOC and COD of OTC. In the optimum condition, Linear model was performed 155 ppm of OTC were removed by 1000 ppm NZVI after 6.5 hours and the removal efficiency of absorption at 290 and 348 nm, TOC and COD were 87, 95, 85 and 89 percent, respectively. In the similar process, there is no organic compound after 14 hours. The parameters ORP, DO and pH were investigated for 6:30 hours to study the type of NZVI reaction in process. In the beginning of reaction, oxidation was the dominant reaction after 3 hours, photocatalytic reaction was remarkable. The mechanism of OTC degradation is proposed by HPLC/ESI-MS and four by products were found. Also the rate constants (first order kinetic chain reaction model) were 0.0099, 0.0021, 0.0010, 0.0049 and $0.0074min^{-1}$, respectively.

• Environmental Engineering Research
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• 제17권2호
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• pp.111-116
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• 2012

This study investigates the complete removal of nitrate and the recovery of valuable ammonium salt by the combination of nanoscale zero-valent iron (NZVI) and a membrane contactor system. The NZVI used for the experiments was prepared by chemical reduction without a stabilizing agent. The main end-product of nitrate reduction by NZVI was ammonia, and the solution pH was stably maintained around 10.5. Effective removal of ammonia was possible with the polytetrafluoroethylene membrane contactor system in all tested conditions. Among the various operation parameters including influent pH, concentration, temperature, and contact time, contact time and solution pH showed significant effects on the ammonia removal mechanism. Also, the osmotic distillation phenomena that deteriorate the mass transfer efficiency could be minimized by pre-heating the influent wastewater. The ammonia removal rate could be maximized by optimizing operation conditions and changing the membrane configuration. The combination of NZVI and the membrane contactor system could be a solution for nitrate removal and the recovery of valuable products.

• 한국지하수토양환경학회지:지하수토양환경
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• 제19권6호
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• pp.80-90
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• 2014

The laboratory and field studies were conducted to identify an optimal injection concentration of nanoscale zero-valent iron particles (NZVI) and to evaluate the applicability of NZVI-based reactive zone technology to the site contaminated with trichloroethylene (TCE) DNAPL (Dense Non-Aqueous Phase Liquid). The laboratory test found an optimal injection concentration of NZVI of 5 g/L that could remove more than 95% of 0.15 mM TCE within 20 days. Eleven test wells were installed at the aquifer that was mainly composed of alluvial and weathered soils at a strong oxic condition with dissolved oxygen concentration of 3.50 mg/L and oxidation-reduction potential of 301 mV. NZVI of total 30 kg were successfully injected using a centrifugal pump. After 60 days from the NZVI injection, 86.2% of the TCE initially present in the groundwater was removed and the mass of TCE removed was 405 g. Nonchlorinated products such as ethane and ethene were detected in the groundwater samples. Based on the increased chloride ion concentration at the site, the mass of TCE removed was estimated to be 1.52 kg. This implied the presence of DNAPL TCE which contributed to a higher estimate of TCE removal than that based on the TCE concentration change.

• 한국지하수토양환경학회지:지하수토양환경
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• 제21권6호
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• pp.192-203
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• 2016

A field investigation was conducted on an aquifer contaminated with trichloroethylene (TCE) for application of in situ reactive zone treatment using nanosized zero-valent iron (NZVI). The aquifer was an unconfined aquifer with a mean hydraulic conductivity of $5.14{\times}10^{-4}cm/sec$, which would be favorable for NZVI injection. Seasonal monitoring of TCE concentration revealed a presence of non-aqueous phase liquid form of TCE near IW (injection well). The hydrochemical data characterized the site groundwater to be a $Ca-HCO_3$ type. The average value of Langelier Saturation Index of the groundwater was -1.33, which implied that the site was favorable for corrosion of NZVI. Dissolved oxygen (DO) concentration varied between 2.5~11.5 mg/L, which indicated that DO would greatly compete with TCE as an electron acceptor. The hydrogeological and hydrochemical characterization reveals that the time around November would be appropriate for NZVI injection when water level and temperature are relatively high and DO concentration is low.

• 대한환경공학회지
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• 제33권6호
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• pp.413-419
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• 2011

본 연구에서는 TCE 등의 유기오염물질로 오염된 현장의 지하수를 처리하기 위한 반응매질로써 나노영가철(nanoscale zero valent iron, NZVI)의 적용성을 평가하기 위해 수행되었다. 오염현장에서는 TCE 외에 음이온($NO_3^-$, $Cl^-$, $SO_4^{2-}$, $HCO_3^-$)과 자연유기물질(natural organic matter, NOM)이 검출되었으며 상업용 나노영가철(NANOFER 25, Nanorion)을 이용하여 모의, 현장 지하수를 처리하고 그 결과를 분석하였다. TCE만을 고려한 처리실험에서 25 g/L의 NANOFER 25는 1.8 mM TCE를 약 20시간에 95% 이상 처리하였으며($k=0.15hr^{-1}$), TCE 반복주입을 통해 평가한 NANOFER 25의 반응용량은 0.19 mmole TCE/g NZVI인 것으로 나타났다. 음이온은 개별 음이온의 농도는 반응성에 큰 영향을 주지 않았으나 4가지 음이온을 모두 포함하는 오염현장의 평균농도로 제조한 모의지하수처리 시 유사 1차속도상수(k)가 $0.069hr^{-1}$로 60% 감소하였으며 총 반응용량은 10% 감소하였다. 용존성 유기물(DOC)를 기준으로 한 유기물의 현장 평균농도에서는 반응속도상수가 $0.025hr^{-1}$로 84%까지 감소하는 것도 확인할 수 있었다. 오염현장에서 최고의 TCE 농도($1.8{\mu}M$)를 가지는 현장지하수를 이용하여 처리하였을 때는 TCE 농도가 낮아 25 g/L의 NANOFER 25를 사용하여 10시간 내 90% 이상의 TCE를 분해할 수 있었다. 본 연구결과와 현장 오염지하수에 대한 수리, 지질학적 조사결과를 접목할 경우, 향후 효율적인 현장 지하수처리 결과를 도출할 수 있을 것으로 예상된다.